I think it's my fault that lisap has typed the word descriptor so many times.
When I think of polished, I think of someone who is impeccably well groomed, wears clothing that fits perfectly and is in pristine condition, etc. Every hair is in place. Makeup is flawlessly applied. You get the idea. I do think there's more than one way to look polished, Attention to every last detail of grooming and dressing is key.
My DH's boss is like that. He looks perfect all the time. I only saw him look less than perfect one time, and that was because he had been out mowing his lawn. He didn't look like himself, you know, because I am accustomed to seeing him wearing a suit and tie.
I do think some people have an easier time looking polished than others, just because of what nature gave them to work with. Some of us have to spend a lot more time on our hair, etc.