The Persistence of Vision web site at http://www.povray.org/ has documentation, tips, tricks, and links to several wonderful resources. The POV-Ray Book Project at http://book.povworld.org/ has a series of projects that guide you to more and more advanced use of POV-Ray. My own Persistence of Text at http://www.hoboes.com/NetLife/POV/ has a handful of detailed projects that guide you through understanding specific concepts in POV-Ray.
If you want to be inspired by what raytracing can do, go to the Internet Raytracing Competition at http://www.irtc.org/. They hold several competitions every year, and keep an archive of past contests going back to 1996. Many of the images there were created using Persistence of Vision. Go there if you are easily inspired, but not if you are easily discouraged.
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