Thank you very much for your replies.
After reading the link from Andrew, it still seems very much a gray area. I think the best way to learn would be putting it into practice and creating a simple site using positioning for everything, just to get a feel for it and see what the results are. It's definitely an area of CSS which I am lacking so i'd like to close the gap.
I'll keep updating the thread with any issues which arise but again thank you all very much for the replies. Seems there are many different opinions on it so it's definitely worth taking a stab at it for future projects. I can seem to get things where I need them using floats with ease but I'd like to try different approaches to gain the same effect.