IMHO Powergamers are those players who try to make the most powerful character permitted by the rules. eg. to create a fighter with minimum intelligence and maximum strength the powergamer chooses a half-orc for even less intelligence and more strength.
Munchkin players will use any exploit/cheat/bug to make their character even more powerful. For example the Exploit Eddie build. When a certain cleric spell is cast it gives you a boost and an extra attack per round. If you cast it three times you get three extra attacks per round. Add that to a dual weilding kama monk with haste and flurry of blows and you get a character attacking 12-13 times per round [img]graemlins/wow.gif[/img]
robertthebard
As for preferred classes: in NWN most of the various races have one basic (non-prestige) class which does not count for the XP penalty.
Dwarves = Fighter
Elves = Wizard
Gnome = Wizard
Half-Orc = Barbarian
Halfling = Rogue
For Humans and Half-Elves, they ignore the highest base class they have.
I am still trying to improve on a Sorceror/RDD/Dwarven Defender build before I post it...