5.1 PCM requires lots of bandwidth to send as a PCM signal - HDMI is one of the only interfaces that can do that.
USB refers to a specific interface and standard, and it carries data in a different manner.
That said, there are audio controllers that can connect via USB and provide 5.1 outputs. For example the X-Fi Surround.
USB based headsets (and 5.1 headphones in general) are generally of inferior quality to dedicated stereo headphones, but there are examples that do 5.1 via USB; Zalman makes at least one.