I had to vote for James T. Kirk I grew up with Kirk and the original cast, and as a kid playing Star Trek with friends, I always played Kirk. That said, if I had to choose a captain to serve under, I would pick Piccard. The redshirts under Kirk did not have that great a life expectancy.
I picked Picard because of the acting quality. Of course I grew up with Kirk and love him as Captain, Picard gains 2 pts for being a better leader and more humble.
Janeway has a soft spot for me as well because she was a woman, but the writing for Voyager was so spotty and convoluted!
Why no Captain Archer? I would rate him higher than Sisko. I never bonded with that show. The lack of ship and all.
Have to go with Jean Luc, only he could pull off becoming a Borg. I think his interaction with Q was awesome. (gotta say Q is one of my favorite characters)