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1. Depending on your pickpocket skill and its corresponding perks you can place the poison on them.(Chance percentage will show once it shows you their inventory.)
2. Slap the poison on a weapon and attack them with it, also take note of what level the poison can affect, if you attack someone who is past level 31 and the poison description says "Only up to level 30 can be poisoned" the poison will be resisted.
You are in good company. The poison mechanics are not that well implemented, and cerainly not clear at all how they work.
To "slap" a poison on a weapon, you must equip said weapon, arm it and then drink the poison. That way the next hit only will administer the poison to the victim. This means that, for example, if you poisoned an arrow and you miss the shot, the poison will be wasted. This won't happen with a sword or axe, but do not think of persistent effects like the Witcher's oils or Diablo's poisoning damage.
Man how awesome would it be if it worked like that.
Well, you're not drinking it, you get a dialogue box asking if you want to poison your weapon, you just activate it the same way as if you were going to drink it, then it handles it differently.