Kurt Angle. I think Orton was more disciplinary for behavior although I may be wrong. There was also that time when they suspended guys like Super Crazy and Lashley because of the hepatitis scare. Let's not forget that the Wellness Policy was really only active for like 18 months and the first tests were just base tests if I'm not mistaken.
Prior to the Wellness Program guys like William Regal, Sean Waltman, Shawn Michaels, Eddie Guerrero, Eugene, Jeff Hardy, Jamie Noble and I believe Brian Christopher at one point were suspended due to worsening drug problems.
Noble was fired because he filed an insurance claim (IIRC for an infected steroid injection site) and specifically listed steroids as the cause on the form, not because of a worsening drug problem.