Hi,
Ideally, I would not even ask the user to fill his substate, but simply restrict my shipping methods per zip code ranges so that if there are no shipping methods found for the zip code of the user, the default "no shipping methods found for your location" message is displayed by HikaShop and it doesn't let you continue.
Unpbulishing all the countries takes only a few seconds since you just have to filter your zones listings by country, increase the number of elements displayed, select them all with the global checkbox and click on the "unpublish" button. If you want it faster, you could write a query in the database. So I don't know of a way faster than that.