If you go into settlement build mode, select a settler and then assign them to the power armour they get into it but immediate get back out of it.
If you leave it near their guard post with a fusion core in it they will get into it when under attack but as others have said, raiders can get into it too if they beat the settler to the punch.
With regard to settlers and ammo, all you need to do is give them one round of the ammo type required by the weapon you give them. This does not apply to companions as they consume ammo regardless of whether they are with you or not.
I've been collecting combat armour, institute lasers and normal lasers to equip all my settlers. Settlements look great when attacked at night, awesome light show. 