Well, "valve job" could mean many things. First of all, a "normal valve job" consists of grinding the valve seats with a special grinding stone, and grinding the valve itself on a valve grinding machine. It also means grinding the stem tops to a new true, flat surface. Typically anymore on a car engine you grind the seats and valves with three differant angles using three differant stones. Once you are done most people "lap the valves in" using a gritty paste on the valve seat called lapping compound. This just finishes the sealing surface, kinda like a polish. They also usually vacuum leak test the valves. And probably if parts (valve springs, valves, etc.) were replaced, the spring "installed height" would be checked and shims placed under the springs to change this.
Thats a basic idea. As for a five angle, use more differant angled stones.(better seal) And will changing valves defeat the purpose of buying heads that just had a valve job? ABSOLUTELY, new valves need a valve job too, to match your seats. (not the ones that your girl sits on)
My question to you is this: why do you want new valves?