As long as nerds come together they will come together to debate who stands alone as the pinnacle Enterprise Captain. May I toss a third name into the debate? William Thomas Riker. (I should note that I have seen this topic discussed elsewhere, but I forget where.)
The debate starts in the season two episode "Matter of Honor" in which Riker is assigned to a Klingon ship (The Pagh) as part of an officer exchange program. Both the Pagh and the Enterprise eventually find an organism eating away at their hulls which results in the Klingons blaming the Enterprise. Because of the exchange program Riker eventually finds himself facing down the Enterprise and successfully getting Captain Picard to surrender. Somewhat of a hollow victory for Mr. Riker, but a victory nonetheless.
Later on that same season in "Peak Performance" we see Riker and Picard squaring off again in a simulated war game with Riker being given the unfortunate disadvantage of the eighty year old USS Hathaway (and Wesley Crusher). Before the games are cut short by Ferengi intervention, Riker manages to score a direct hit on the Enterprise. Later on to escape the clutches of the Ferengi, it is Riker's genius that is the lynch pin of the plan, not Picards. Will is looking pretty good and it won't be the last time he outwits Picard with inferior technology.
The most compelling case in favor of Mr. Riker is perhaps the events around the Battle of Wolf-359 in which Picard is captured by the Borg. The field-promoted Captain Riker is able to outwit the technologically superior Borg collective with Picard at the helm to not only save earth, but to save his captain as well.
Then we come to the movie Insurrection. While Picard is down on the planet dillydallying with centuries old alien babes James Kirk style, Riker is making a run for Federation space while simultaneously beating the shit out of the Son'a. Picard winds up polaying a glorified game of hide and seek while Riker blows two Son'a warships to pieces with nothing more than his massive testicles (and explosive space gas).
And where are they now? If you follow the novels, William Riker Captains the USS Titan with Christine Vale as his First Officer and Deanna Troi as his second. The USS Titan ends up engaging the Caeliar, the race that inadvertantly caused the birth of the Borg Collective and ends up reabsorbing the Borg into their benign group mind. Where was Picard and the Enterprise? Meeting the Borg invasion fleet, suffering the greatest losses every Alpha Quadrant race had ever seen and watching several Federation Member Worlds obliterated or charred beyond recognition, among them Vulcan, Qo'nos, Andor, and Tellar. Oh, and knocking up Beverly Crusher. (Wesley Part II!!!)
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