Whether you started your SharePoint 2010 development already or will start later when the product is released – have no doubt - you will be making UI and branding customizations.
Check out these few screencasts (find the ones related to branding) of my own which had some incredible popularity and see how you can get started with branding your SharePoint
Here are few more good resources on the topic:
Part 1: http://singchan.com/2009/12/23/branding-sharepoint-2010-collaboration-sites-part-1-in-a-series/
Part2: http://singchan.com/2009/12/29/branding-sharepoint-2010-collaboration-sites-part-2-in-a-series/
If you’re interested about SharePoint branding check out my new book titled SharePoint 2010 Branding in Practice: a guide for web developers
Enjoy!