I think this is an interesting question, Rather than, "Which Captain do you want to be?"
Who would you most want to serve under? Who would you like to take orders from? Who would you trust most to get you home safe? Why?
This is regardless of the ship, only the captain. I have limited the choices to the five series Captains and Spock since he was Captain of the Enterprise for awhile in STII.
On second thought, I'll throw Pike in there too.
My Choice would be Picard. There is something about him. He is a very strong character, he inspires confidence in his crew, demands respect, yet encourages expression and does not stifle his crew. Tactician, Diplomat, culturist, and he knows how to have a good time.
So what's your choice?