Nephalem Valor is only obtained once you reach level 60, and only stacks up when you kill a full pack of Champions (blue named mobs) or a Rare (yellow named mob, usually with minions). Purple named mobs such as Unique mobs and bosses don't stack the buff. Each stack gives an additional 15% Extra Gold and 15% Magic Find. Stacks to 5, lasts 30 minutes since the last stack was applied, and disappears if you leave the game or swap ANY skills/passives.