I'm voting him vs kirk because I have only seen the original and next gen. I enjoy the first series as equally as the next gen, but I like Picard's character a little more. A bit more strict, but also quite personable.
Favorite episodes of both would be the trouble with tribbles in TOS, fav scene when Kirk is talking with Scott on "Who threw the first punch", and in Next Gen is when Picard was invited to the Admirals Banquet and he was trying to find a way to avoid going when the ship gets infested with metal parasites. He managed to get lucky in his excuse, making it his seventh avoidance of the banquet!
I vote for Picard, with Kirk in second place. The others I cannot vote on because I have yet to watch those series, but can't spare the time anymore. wish I could, but I can't.
Also, I like his accent.