Gryffin, I like your point here about perfection and our eye for the unexpected...maybe a better word than "effortless". Many years ago I bought an old antique Amish quilt and one square looked like it was a mistake, but turns out they did it on purpose of course, as they believed only God was perfect.
But back to clothes. Sometimes when I see someone in an outfit that looks too planned, maybe too matchy matchy, my eye wants to add something imperfect too...like you say, rumple their hair or lose the pearls, as if they have just come from an afternoon of great sex, not to get off color about it, but just, well, that relaxed feeling one has in their body, the ease of movement. Maybe "effortless" is used too though because sometimes one looks so pulled together it can appear and feel too controlled and kind of uptight to use an old word...instead of using clothes to express the relaxation and joy in the body, even if one is at a dressy event.
That said, I feel everyone should do their thing, and discover their own artistry. That after all, is the fun of it, isn't it?