OK. The Invoicing tab is the master location for assigning a tax group to a customer. Indeed anything set here would be used for new customer invoices.
What you did should solve the problem. If you needed to check if there were any more, you could search customers using the SmartFinder, add the Tax Group field to the grid, and search for all customers that have a tax group not equal to blank. Just so you let the program do all the grunt work for searching.
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Regards,
Softrak Tech Support