Let's include the usual suspects: Kirk Picard Cisco Janeway Archer If you want to include Spock because he achieved the rank of Captain or Sulu because he commanded the Excelsior or any other captain/commander of any starship/star base/space station, that's fine too. (I really liked that Commodore Wesley...but I really don't want to serve under Commodore Decker ) If you're a Starfleet officer, which captain would work best as your superior officer? It's not necessarily picking the best captain. There may be someone on the list you consider best but recognize that with your personality and theirs it would never work. Look at your personality and pick the captain that you would work the best with. As a viewer I like Kirk. Would it work for me to serve under him? Not so sure about that.