There are a huge number of funcions available to Python scripts in ArcGIS. You'll probably never need most of them and there are many that effectively do the same thing. So, like the toolbox, one of the greatest challenges is just to find the function that does what you want.
Functions are organized in somewhat the same way as the toolbox with another set of functions specifically for scripting. Below is a list of the libraries you'll probably use:
Most of the other toolboxes are represented as well and you can browse them by typing "arcpy." in Wingware or the in the Python window in ArcGIS
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