Definitely Picard over Kirk as my choice for captain, though you are right, Kirk did all right for himself in the movies. It's the cool, calm, control vs the rules-bending cowboy. I would feel more comfortable with Picard in charge of the ship.
But if we are talking about sex appeal ... then give me Worf! :)) Though not the tense Worf of early TNG, I want the man who fell in love with Jadzia in DS9....
I don't ask for much, do I?