Can be done easily in a local match with a second controller, or in a single fight on very easy difficulty. Set MATCH TIME to OFF under gameplay settings if you think time will be a problem.
Select Batman as your character, and your opponent to any character. Press START to view a quick reference of all of Batman's special moves.
Make your way down the list, performing each special move at least once during the match. Note that none of the moves need to hit the opponent. Remember to use his character power (B button) as this appears to count as a special move as well.
A supermove requires a full meter to execute. It's possible to KO your opponent before building enough meter, so use special moves without hitting your opponent to build meter. Up Batarang (Down, Back+Y) is thrown up in the air so it won't hit and kill your opponent. Once you have enough meter, press LT+RT to do your supermove. Finish off your opponent to unlock the achievement.