I too must go with Kirk.
He was the master tactician, and he did whatever it took to win, he could never except failure. A perfect summary of his mentality is the otherwise awful Star Trek 5(with Spok's brother and the search for "God"), which talked about the exam Kirk had to take at the Academy, with the situation that was impossible to win. It was designed to teach the student to accept loss. Kirk, being the clever bastard that he is, cheated, and passed.
Yeah, and he got the girls.
Second in my mind would be the philosopher Captain, Picard. Janeway would be third. Sisko I never thought of as a Captain, because he wasn't very battle-tested and he worked from a space station, not a ship. However, there's no question that Sisko had the coolest voice. :)
