I have a DVD set that says it has a US federal exporting restriction due to its content about firearms. I want to be as sure as possible that I only sell it to a US accountholder. I made a "business policy" with applicable shipping country exclusions and picked that policy for the listing. Will this indeed exclude all buyers outside the US?

Not necessarily since the Business Policies is a fancy word for 'auto bot system' and since you probably listed that item under DVD's and not Weapons (or close). You can just 'exclude all the countries (check them all)' for that particular item in that item, and not use Business Policies

Excluding one listing from EIS - did I do this right? | Shipping

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Excluding one listing from EIS - did I do this right? | Shipping | eBay Community