Sure, you might be the toughest, the fastest, the slickest one in the room. But sometimes you need a little something extra to get you out of a tight spot.
That would be Luck, the final attribute in Fallout 4's S.P.E.C.I.A.L. system. Without luck, your well-placed shots may still miss. Or you might not find anything in that treasure chest but toenail clippings and some rusty nails.