Yes - I even thought of building boxes near guard stations, where better weapon and a bit of ammo go to be taken in case of attack. But I do not think this works really well - better to equip them myself. The trade menu is new - Beth built it for a reason.
Also I think, that settlers are best served with good but 'normal' weapons. I think, a bonus from Legendary weapons and even some of the mods do not help, when a NPC uses the weapon. Generally I see them often use weapons in hip fire mode, so I give them weapons good for both, hip fire and exact shooting. I also think, that better sights do not help. But since I gave them normal combat rifles, combat shotguns and laser muskets they are quite deadly, especially when 5 of them are shooting at the same enemy.