Traditionally, most paint used by house painters was some shade of white. The wearing of white is simply because it does not contrast and show up the paint drops and splatters that are part of the days work. Blue Jean painters look pretty sloppy after a few days of painting, and less likely to be hired.
http://painterforum.com/white.html
Nobody seems to know for sure how the practice started, but there are a few theories about why “whites” made sense. In fact, the International Brotherhood of Painters and Allied Trades, posed the same question to their memberships.
One advantage that just about everyone could agree on is that white connotes cleanliness. A painter, after all, removes dirt and crumbling plaster before applying paint. Many painters compared the purity of their “whites” to the uniforms of nurses, chefs, and bakers. Philadelphia One painters theory is that a white uniform is like a badge that says, “There’s no paint on me, so I’m doing a my job.” Obviously, it is as hard to hide paint smeared on a white uniform as it is to hide a ketchup stain on a chef’s apron.
http://charmville.com/painters.html