Microsoft has created a tremendous amount of technical documentation on PowerShell and has placed this on-line. Here's some of the documentation you can get:
- Windows PowerShell Getting Started Guide: http://msdn2.microsoft.com/en-us/library/aa973757.aspx. This document is designed to introduce new users to PowerShell and to provide an introduction to the basic features.
- Windows PowerShell Programmer's Guide: http://msdn2.microsoft.com/en-us/library/ms714674.aspx. This document is aimed at developers who want to provide a command-line management environment for systems administrators.
- Windows PowerShell SDK: http://msdn2.microsoft.com/en-us/library/ms714469.aspx. A guide for cmdlet or provider developers.
- Windows PowerShell - Managed Reference: http://msdn2.microsoft.com/en-us/library/aa717491.aspx. A detailed look at the classes provided by PowerShell.