So let's step through it slowly (sorry if this is painful and sounds overly simple, but you got a problem right). You have the item in the characters inventory. You select the character and the Use / Give button. This brings up your item list at the bottom. The default of the list is always to Use (highlighted in Blue). You left click on the list words to change this to Give. You scroll through the items till you get what you want, then you get up close (should have blue circle for mouse pointer) and left click on the NPC.
Is that a detailed description of what is failing?
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