I don't generally dabble in Pickpocketing, but recently decided that it may be a wise investment of my time to give some townsfolk a bit of reliable gear. My problem is not with weapons, but the apparel; how do I go about getting NPCs to equip things such as upgraded armor, enchanted rings, etc.? I thought I read somewhere that it was entirely possible, but never looked further into it than that since, as I previously mentioned, I don't use Pickpocketing.

If someone would be so kind as to enlighten me on the ins and outs of the skill, I'd appreciate it.

From what I know an NPC will equip anything better than their current stuff, if they don't then put it in their pocket then steal their original items so that they have to use your equipment.

Don't bother. While NPC's do equip armor and jewelry you give them, as soon as you leave the cell and return, they revert to their default gear.