Depending on your needs, we have several great "getting started videos" available online:

Using Pion to Capture and Replay website visitor sessions:
http://atomiclabs.com/pion-web-analytics/demo-replay/

Using Pion for Web Analytics (high-level):
http://atomiclabs.com/pion-web-analytics/demo-tagless/

Using Pion with Omniture:
http://atomiclabs.com/pion-web-analytics/demo-omniture/

Using Pion with Webtrends:
http://atomiclabs.com/pion-web-analytics/demo-webtrends/

Note that integrating Pion with Google is very similar to Omniture, and integration with other vendors like Unica is very similar to Webtrends.

Our user manual has a wealth of more detailed information, which you can download from here:

http://pion.org/files/pion-platform/platform/build/pion-manual.pdf

Our sales staff is also available for demos, to personally step you through getting started and answer any questions you may have. We normally assist customers with the initial implementation of Pion and also provide training. If you downloaded the enterprise edition of Pion, someone has likely contacted you about this already.