I built all my PC's. In fact, my music computer was originally the best parts of 3 broken PC's chucked together and held up with gaffer tape!
My only bit of advice (as you said you know about computers) is ALWAYS wear an anti-static band, even if you don't plan on putting anything into the case just yet. I mean when handling new components and getting them out of their anti-static wrappings etc. Also, NEVER touch anywhere but the sides of the motherboard / ram / CPU / PCI cards.
Oh and another thing, try not to let any of the fans move around when the computer is off. They generate their own charge when they aren't powered if they are spun with your fingers or other movement, and without the power regulation of the PSU, you can easily short other components by building up static charge in the fans.
Apart from the physical side of building PC's with all the precautions you should take etc, building one is usually a painless affair. The only thing I curse every time I have to do it is putting the damn CPU heat-sink fan on. No matter what system the thing uses for coupling it to the motherboard or chipset, it's always bloody difficult. They are by far the most awkward, stupid, lamely designed parts of the computer system to install and are the bane of my entire computer building history. The only advice I can offer here is have a punch-bag set up nearby. It might save you from having to buy a new computer and a new pane of glass for the window you just threw it out of. :x :x :x