Hi Martyn,
I myself went from reseller shared hosting to
VPS Hosting a few months back. It has been a steep learning curve initially but once you get familiarised with everything, you soon are able to understand and do most of the common things on your
VPS Hosting. I was on to support initially a lot getting things set up as I wanted/needed them but after that, it's just odd bits and pieces.
If you want to know more about the move and things, drop me a PM.
Jonathan