In an ideal (CoH) world, I'd like to have zero overlap between powersets among all my toons. That means no matter how many toons I make, I can only use a powerset once. So for example if I make a Kin/Sonic defender, I can't use Kin or Sonic Blast on any other toons. I mostly stuck with this idea in the original CoH, and if we get it back, I'd like to do it again, but with a lot more planning, due to a lot more knowledge.
With a clean slate, I've come up with a choice for each AT, and the goal is to maximize power/effectiveness...basically to find the best combos from what's available.
I don't generally do the "best" thing, but its a fun premise, so I'm game. I liked to try to play everything, but I didn't have a no overlap rule myself. Still, by these two rules (no set overlap, looking for most effective - by at least some measure - combos) and sticking with I23 sets (this changes dramatically in I24):
Blaster: Fire/EM. Very high damage, and still some utility in EM. Sonic/EM would be a better soloer, but its hard to argue Fire/EM is reasonably survivable and very high damage. AR/Mental is the AoE monster, but difficult to make workable until you massively IO it out.
Controller: Illusion/Radiation. In my opinion, the best all-around swiss army knife controller. Good control, good buff/debuff, good healing, pets, and one of the best tier 9 powers in existence.
Defender: TA/Sonic. Its hard to pick the best defender primary; they are honestly all good in different ways. But I really like the utility and diversity of Trick Arrow, and Oil Slick Arrow is just awesome. Supplementing that with Sonic helps overcome Defender's lower damage modifier with high resistance debuffs. And in case of emergency, just break Siren Song's glass.
Scrapper: Kinetic/Willpower. I love, love, love MA/SR. However, in keeping with the rules, Kinetic/Willpower is an extremely powerful Scrapper. */Shield has a lot to love, but in terms of sustained continuous destruction its hard to beat Kin/Willpower. A lot of people denigrated Power Siphon. Those people were wrong. There were lots of other contenders here, but I needed to save them for other archetypes.
Tanker: Shield/Stone. Shield is one of the best all-around defensive sets available to tankers, and I really like Stone melee on tankers with all the knockdown. Its strong defense plus strong offensive mitigation making a tanker that can stand up to a lot of attackers. Note: in I24, I would have rolled a Bio tanker. Bio was going to kick serious ass:
https://www.youtube.com/watch?v=a6bkyUXYlNU&list=UUkyaL-2ZrJKmVBhTkHHUKvg.
Brute: Staff/Dark. Dark is a very strong defensive set, but it does have an issue with endurance. Staff's modes help out greatly in that area. Form of Soul provides endurance discount which can help power Dark, and when that's no longer needed Form of Mind provides a recharge buff which can help keep fury up *and* it also increases the power of Dark Armor by recharging Dark Regen faster. This would make a good single target brute and a great AoE brute.
Corruptor: AR/Kin. Kinetics needs no explanation. I think AR works really well on Corruptors because its AoE heavy: to get the most out of scourge the enemies need to be at lower health. Strong-hitting single target attacks tend to gain less out of scourge than lower hitting (per target) AoEs because the individual targets are at low health more often.
Dominator: Mind/Psi. Psi is a decent attack set and honestly the playstyle options Mind control offers are difficult to give up without using the set somewhere. Plant/Earth would have been my second choice here: unusual play options, powerful sets, and in particular a secondary with power boost.
Mastermind: Bots/Time. I think Time was one of the more underrated sets and it was going to show up somewhere, but overall I believe its best place is in the mastermind. It has a lot of interesting effects that can help pet survival which is important for masterminds. And while there are pros and cons to all mastermind pets I think the good ranged offense of the Bots was most effective in the most circumstances. For those that like to get up and close, my second choice (and the MM I played the most myself) was Necro/Dark. When you're spamming TG and running tar patches all over the place you don't miss Kinetics much. But you have to like knife fights in phone booths with that combo.
Stalker: DB/Nin. Dual Blades is a very good set in general, although other sets outmatch it in certain areas for most other archetypes. But for Stalkers it has a very good balance between single target output and AoE (by virtue of Sweeping Strike being a short ranged cone with high DPA). You also want to avoid sets with DoT (like Spines) or sets that have odd effects that can mess up placates (like Electric's chain effects). Ninjitsu is another highly underrated set by many, although its strength had supporters. But to put it in these terms, if Ninjitsu was handed to Scrappers, it would be among the most powerful scrapper secondaries in existence (almost as easy to soft-cap as SR and with a strong reconstruction-like heal). Its version of PB also had psi resistance, which SR scrappers would have killed for (to deal with non-positional psi). About the only thing SR beats Ninjitsu on is defense debuff resistance (which is incredibly high on SR, making it an excellent set to run things like Incarnate content with). On stalkers, low health limits Ninjitsu from being as powerful a set as it could hypothetically be on scrappers or brutes, but its still plenty powerful.
I was not as much of a fan of /Ice on stalkers because of the peculiarity of the lack of Fire defense. Ice Armor has defense to Smash/Lethal and Energy/Negative, but not Fire/Cold. Many fire and cold attacks were also smashing or lethal, so this wasn't a big deal in terms of overall damage, but the nasty problem with lacking Fire defense on a stalker was that Fire tended to have DoT that would spoil or break hide. So while that Fire defense hole wasn't fatal in terms of allowing damage to land, it could have an outsized annoying effect of compromising hide. In the latest iteration of stalkers hide mode was not as critical as it was previously, but it was still a trade off worth noting between Ice's otherwise strong defenses and endurance management.