the first wiimote you used is synced as the main controller for the wii. to use the madcatz as player one,
1 press the home button
2 goto wii remote settings
3 point on reconnect
4 then press 1+2 on the madcatz until the the wii picks up that controller as player 1
to set both controllers, as above but press 1+2 on BOTH CONTROLLERS AT THE SAME TIME. this is tricky but it works.