You want to work on your car safely, of course. If you're working with corrosive substances and strong cleaning agents, it's a good idea to wear work gloves. Safety glasses are also a good idea in that case. Anti-static shoes with composite toe caps and anti-perforation soles are no unnecessary luxury when replacing heavy parts such as brake discs.
You'll find these and more protective workwear from brands like Sparco, Milwaukee and Sonic at Winparts.