I had to validate an XML against XSD just one time, so I tried XMLFox. I found it to be very confusing and weird. The help instructions didn't seem to match the interface.
I ended up using LiquidXML Studio 2008 (v6) which was much easier to use and more immediately familiar (the UI is very similar to Visual Basic 2008 Express, which I use frequently). The drawback: the validation capability is not in the free version, so I had to use the 30 day trial.