I'm almost complete with the Character Rigging and nCloth Workflow tutorial

but I come across this problem no matter what I try to do with the weight paints.
Some joints won't even be painted on with the tool.

I've tried replace and add but the face still pulls across when I move the rig to paint.

What could the problem to why the face is so ascrew? Even when I've painted the joints to not affect those areas?