i don't see anything wrong with going against cpu after you have just checked out a char... its useful to slowly train yourself and apply moves to really simple, standard situations like poking, punishment, combos, spacing etc. whatever your character does. sure you can't play mind games with the comp but you're character is going to be so damn basic that you won't even be thinking about mind games anyway. i do think cpu is usless after this stage though.
i personally start by looking through the movelist just to familiarise myself with the char, then check out top 10 move lists and more importantly read why the moves are good. ill also have a quick look at some basic combos just to get me started. ill then move onto the cpu on a setting like hard (yes hard, not edge master) because i want to get down the absolute basics of the character. ill spend more time fine tuning, learning staple combos until im a little more comfortable with the char.
ill then move onto human opposition and try my shit out there... you'll most likely hit a load of walls and there will be many holes in your game but then this is where you go back and learn about the specific stuff you failed on. i'd check out some match vids at this point see how they are played and for fresh ideas then work that into my game.
once im comfortable with the staples, when im at a point where i do stuff without thinking ill start moving onto mind games, tech traps, wakes, cf game etc.... this is probs the point where your style starts getting devloped because you can think and react rather than stall and panic.
then you just slowly develop and learn as new stuff happens, maybe start looking at frame data, character specific strats etc.
i don't know if that fully answered your Q as i realised i was more talking about learning a character than 'moves'. i think the most important point is to learn why a move is good rather than just being told its good.