when should i usually build a second capital ship? i find that it's difficult to wait for the resources to accumulate while i am trying to colonize, develop planets, and build frigates and structures
Very much so; it's difficult to save up for a second capital ship early on, and it requires some very careful penny-pinching to pull off. You have to find little scraps of money you can save at every turn, and then push out that capital ship and put it to work immediately. If you can level it up quickly enough, two capital ships can give you a big advantage in battle, but this is a risky gambit since an enemy who puts that money into economy or fleet can overpower you in the short-term.
which is better to build in the late game, assailants or enforcers
Depends on several factors. Generally assailants have more firepower (those awesome phase missiles) while enforcers have more durability. If you can keep bombers out of the picture with the Kortul's jam weapons, then enforcers become very good. Overall, you won't be disappointed with either unit.
similarly, should i have more overseers or subverters, subverters aoe disable ability is cool but its so expensive to research the prototype and the ability...
Subverters are one of the most awesome units in the game. They do come very late in the game, and that makes them quite expensive, but they're well worth your time. As for a precise mix, it really depends on what you're doing. One is a strictly defensive unit, the other is a strictly offensive unit. You do want both, but it depends on what kind of flavour you want for your fleet as to which one you prioritize.
the optimized construction upgrade (4%/8% ship and structure cost decrease) does not appear to stack with enslaved labor
Enslaved labour lowers credit cost, optimized construction lowers metal/crystal cost.
This is really only useful if you're trade-spamming and need to buy most of your resources from the black market. If you're still selling to the black market, don't bother with this tech.