Any captain discussion outside of Kirk & Picard (and maybe Spock) should be disregarded as blasphemy. All the major characters think so.
As far as I'm concerned, only two Captains should be considered for the role of 'Best Captain'. Sure, they all have their merits, ranging from founder of the United Federation of Planets to interquadrant rescuer to Dominion warrior... but really now. Kirk & Picard have each saved the galaxy more than the rest of the captains on this list combined (though Archer did have a good, albeit short run). Kirk is cunning, spontaneous, and has an unbreakable spirit. However, considering the various hardships & diplomatic achievements Picard has gone through in his not-yet-completed career (highlighted by his first contact & assimilation by the Borg ... and don't get all trekkie on me and say both Archer & Kirk met them first, those are technicalities), my choice is no other than the balding ambassador from La Barre, France.