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If you're confident enough in your level/ability, the survival mode for multiplayer is a decent way to build masteries, since you can solo it and it uses single-player character data. (I'd recommend at least getting to level 12 before trying this, though.) Yin and Yang aren't too hard to grind up, but Flash can get difficult since you don't have Ninja Arts. And any characters that have poor combo abilities will take longer to level up, normally and for masteries (since XP seems to take combo into account).
I'm afraid I'm can't help much more. Getting more than one mastery on a single character is a project of devotion to that character, due to the heavy grinding. I don't remember if SV or EV had the trophies for finishing all three, but those trophies allow for different characters to be used and it's best to do it that way if you only want the trophies.
Maybe someone else has a better idea how the system works, though. Mastery doesn't seem to be 1:1 when compared to XP, so maybe there's a way to game the system.