PSP is very simple to use once you know how. Having knowledge of MS Paint will help you. It's hard to write much down as it's such a diverse programme. I suggest that when you start a new piece (the white page button) that you change your background to transparent (it will either come up as an option when you first use the programme, or as a tick box under the size of new image boxes. I'd keep the size small to begin with to get used to it as then you don't have to zoom in and out consistantly (like 500 x 500 pixels). Just try things out, like drawing, filling, picture tubing. I suggest you untick any vector boxes as you'll have to merge the layers afterwards if you want to post your pics anywhere (the layers such as vector tend to sepatae in certain formats and you get 3 pics. Try out raster layer..they're great for not interupting pics on another layer...get rid on antalias too as it can be a pain to draw with like vector. Make your brush density 100, as the fuzzy edges cause problems filling (unless your goinf over the top of a drawn image and want a fluffy edge. Remember fill won't work is there are any holes so look carefully if you do that....
Yeah this will prolly make no sense..but just play and you'll understand what i'm saying..i learnt psp all by myself..you'll get stuck and wonder why your fill sloods everything and not just the area, but just ask or search the net. you'll find out then you need you fill to be set to RGB Values...if you get stuck, you can PM me, but seriously, just play and enjoy ^-^