1) Drawing formats - Paper size, company logos, title blocks, tables with model specific parametric input (default tolerances, materials, heat treatment, etc.)
2) Drawing templates - default views including sections, dimensions
3) Part templates - initial features(mostly named datums), named views, sections, parameters - very useful, think this through, can be used to populate drawings.
4) Assembly templates - same as parts
5) config.pro - hundreds of settings controlling Pro/E behavior at startup. There are multiple standard locations for config.pro and you can load additional files on demand. These config settings can be overridden. You can also create & store mapkeys which are macros to execute multiple commands with simple keystrokes.
6) config.sup - Same as config.pro except only one location and anything set in config.sup can not be over written. Use with care and forethought. Don't put too much here. Company name, some config options on file saving maybe. DO NOT define mapkeys here or you will be limited to only one mapkey.
7) creo_parametric_admin_customization.ui - Defines the look of the screen and menus. I would stay away from this until you know how to use the standard layout.

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The Help for this program was created in Windows Help format, which depends on a feature that isn't included in this version of Windows.