To create different UV sets just use the Create empty UV set option in the UV Texture Editor and then use Set Current UV set to move between them.

Remember to practise a bit moving around the UV sets before you dive in, they are actually quite easy to use you just have to get used to it.

I remeber that with one model I worked on I made multiple UV sets and used Multiple texture maps for the one object, I had to use the relationship editor to link the textures with the specific UV's I wanted to display I also used a multilayered shader and made sure I linked each texture's alpha into the multilayered shader.

It was kind of complicated and a bit of a pin in the arse but it worked.

Although I am guessing there is an easier way to do this!