I've painted things apart - just hafta be careful! it does help to assemble everything when primered to get the fit right - if the 'tweaking' is done before the painting then the final assembly will be smoother - the hood just needs 3 people to be a piece of cake - re-installing the glass is where have to take the most care!
as for painting under the hood w/ the engine out - the inner fenders and frame are black, not body color, so you still have lots of masking to do that'll result in a job that looks like a repaint, not fatory, which was done piece by piece - also the firewall needs body color right down to the floorboard, further than you can get when it's on the frame
Bill