In most circumstances (collar spread, tie space, fabric) a Windsor knot is boring--like you've just learned to tie a tie. The asymmetry of a four-in-hand tends to look like a conscious choice--like you've actually chosen each element of your wardrobe, right down to the knot. The four-in-hand also better supports a sprezzatura look. A businessman may use a Windsor: but a gentleman will use a four-in-hand.
I tend to use a double four-in-hand--a look I shamelessly borrowed from Roger on Mad Men. I forget the episode, but he's getting dressed and flips his tie around twice before knotting. I found it roguish.