You just place it in your helmet slot, like you would with a regular helmet.
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You cannot tame an Enderman in Minecraft. If you don't look at them, they will not attack you though. If you wear a Pumpkin on your head, they will not attack you, regardless if you look at them. But be warned, if you hit them, they will attack you.
You can grow pumpkins which can be used to make pie (suger, egg, and pumpkin), and can be used to make jack o lanterns which are glowing pumpkins that can be placed underwater (pumpkin and torch) and you can also wear then on you head to prevent endermen from attacking you (however it provides no protection from damage).
You can get pumpkin seeds randomly in chests in dungeons in Minecraft.Pumpkin seeds in Minecraft can be crafted from pumpkins in the crafting grid.
Put a pumpkin in the crafting table or self crafting
you take some pumpkin suger and a egg and put it anywhere you want in the crafting grid