If you want to add a new country VAT rate go to the left menu under Settings and click the sub-menu Products. Choose the product for which you want to add a new country VAT rate or add an exception, simply click on it.
Scroll down in the pop-up menu and click the option below:
Now add the country and the VAT rate type, the VAT rate type is Standard, Reduced or Zero. Find out more about the vat rate type and all the vat rates in the European Union.