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Your unarmed skill, like all other weapon skills, has a maximum of 5x your level; therefore you can only complete this achievement at level 80. Getting that last point from 399 to 400 takes much longer than going from 398 to 399.
Weapon speed for unarmed is 2.00, but you can speed this up by using a Fist weapon instead. Right-Handed Brass Knuckles, sold in Darnassus, Ironforge, Orgimmar and Shatthrath, are probably your best bet since they cause the least amount of damage, so you can get more punches in.
You can skill up on mobs far below your own level to prevent the damage that you would take, but you will get fewer punches on them before they fall down. The best method once you reach about level 60 and beyond is to go to a secondary starting area with your faction and attack level 15-20 mobs while making sure your PvP flag is down. These mobs will stay up long enough for you to have a good chance to level your skill without them doing any serious damage to you, while at the same time members of the opposing faction cannot take advantage of your unarmed state to score a quick gank with little risk to themselves.
What does not work
- This achievement counts towards Master of Arms achievement, where you have to max 4 weapon skills.
- Filled unarmed skill can sometimes be useful, at least for melee classes.
- / Patch 4.0.1 (12-Oct-2010): Converted to a Feat of Strength.
- Patch 3.0.8 (2009-01-20): you can no longer skill up weapons on mobs that are immune to damage.