Even though you can now add a field of type GUID using AddField_management you can't calculate that value with CalculateField_management. That functionality has been added to ArcGIS 10.0 but does not currently exist and is not considered a bug by ESRI support. I'm suppost to upgrade as soon as possible to get around this even though 10 isn't out.
Anyway, we won't be upgrading to 10.0 until SP1 is released so that maybe 8 or more months from now. I need a workaround for my 9.3.1 server. Any ideas?