Yeah, ok... my bad! Home Premium...
Anyway, come to find out the upgrade to Win7 Home Pre, solved the problem after all. Well, for the most part. IE8, Safari and Adobe Reader now print multiple copies of a job. But MS Works and The Print Shop 23 (uses this to create a 35+ page catalog) will not... no matter what.
I told the client to get rid of Works and Print Shop 23 and get a full version of MS Office 7. Maybe even download OpenOffice, just to see if it would work properly as well, then use it.