What kind of behavior are these captains exhibiting that constitutes unsportsmanlike conduct? I assume you mean behevior performing "captain" duties which would not apply to regular players.
I don't want to write a book, so I'll try to give some brief examples:
Certain captains always try to manipulate the system and re-schedule matches at the last minute when they can't field their "best team". They harass other captains at work and by email if the other captain won't comply with their request. The lengths that these captains will go to to get their way is incredible. And it's always the same captains every season. One captain went so far as to file a a grievance when another captain wouldn't re-schedule a match for him because he couldn't field a team on the scheduled match day. The grievance committee ruled against this guy, so he filed an appeal. The appeal committee also ruled against him. He actually called all of the grievance committee members and harassed them because they ruled against him. Some people have no shame.
Captain A "staged" a big confrontation and argument about line-ups before a match with Captain B's team to purposely try to get Captain B's team so riled up they would get rattled and lose the match. The league coordinator happened to be at the match (unknown to Captain A, who staged the scene), and witnessed the whole thing. The plan backfired, and Captain A's team lost. Captain B sent an email complaint about Captain A's behavior and his teams behavior, and he copied Captain A. Captain A replied to the league coordinator that none of this happened and Captain B made up the whole thing. He said he didn't even know what Captain B was talking about. The league coordinator replied that he was at the match and saw the whole thing. Captain A was busted, but still insisted that Captain B was to blame as much as he was. A player on the Captain A's team later admitted to the league coord. and Captain B that it was all a set up in an attempt to win by rattling the other team.
I could give more examples, but you get the idea. The captains don't necessarily break any specific rules, but they always have controversy surrounding them and cause big problems with other captains. Everyone knows who these captains are, and most people cave in to their requests to avoid drawn out confrontations. Most people simply don't have time or energy for that kind of stuff. I think these captains should be suspended by the league coordinators if the LC's get enough complaints or witness the incident.