There is actually a wealth of MPLS white papers on Cisco web site. Please use the search engine to locate the one you want. Let me know if you don't find what you need.
For a purely introductory look at IPVPNs as a whole along with MPLS VPNs and what they can do for your organisation you can go to http://ipvpn.telewest.co.uk/telewest/what_is_ipvpn.jsp. However, for more in-depth technical overviews either search on the website or look at http://www.ciscopress.com. The Cisco reference books cover the subject in-depth.
The MPLS Resource Center (http://www.mplsrc.com) has a wealth of papers including an MPLS FAQ. There is also a very active discussion list for MPLS operational issues.
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