PVR'd while on Loan Service 9 years after becoming Spec Aircrew, having thoroughly enjoyed 2 years in the Army and 26 in the Royal Air Force. Had absolutely no problems as my 1st RO was very understanding (ie he was leaving at his next option) and the rest of the LS crowd didn't care a hoot. Left the equatorial Fantasy Factory the day after 11 Sep 01, arguably not the best time to start job-seeking as a pilot.
PVR = one of the best work-related decisions I ever made. I put the Resettlement system to good use, and can highly recommend the advice doled (har har) out at the Uxbridge centre. Didn't have to apply for any of the jobs I didn't fancy at the time (N Sea, Africa) - found gainful employment before my time was up.
The advice given above about the first job being the real resettlement is sound. In my case, I only really found this out when I took up my second job (still with the same company, but overseas). It was then that I realised how lucky I'd been with the first choice! Make sure you know what you're trying to achieve by seeking work and a way of life outside; I now know that - while the money is nice - I'd rather keep the quality-of-life factor uppermost. I still get to see more of the family than many of my Odiham/ Benson contemporaries though, which makes it worthwhile.