First you have to collect armor
then you have to find settler and then try not to mix up your character's stuff with the settler's.
Would be easier if stuff in the workbench could be tagged:
ID tags: Shopkeeper(including scraqer), Farmer, Sniper guard(tower), Closerange guard (shotgun, auto- and melee weapons)
So stuff in the workbench will be tagged with work-role, and the settler is supposed to get his gear when assigned a work.
(Btw: best FO game of all wasteland games yet!)