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Hi Andy,
Firstly,
welcome to the wonderful world of XOOPS :)
The FAQ here (pointed out above) has a lot of information about getting started with XOOPS theme creation, including a dissection of the default theme, as well as links to other helpful information, including a Flash tutorial.
If you are a fast learner & prefer to learn as you create, you could probably bypass reading all that & start with
MyXoopsExtensions, available for Dreamweaver MX as well as Dreamweaver MX 2004.
The
MyXoopsExtensions FAQ should contain enough information to help you get started creating your own XOOPS themes today.
Best of luck with your XOOPS!