If I understand correctly, I can use the this one time and style all controls in an application or form....question is, how do I do that
Yes, that is correct. AppStylist allows you to style all of the control in your application at once.
If you are not sure where to start, I recommend the online help.
NetAdvantage® WindowsForms Online Help :: 2009.2
Look under Developer's Guide-->Styling your Application-->Application Styling Framework