I'm back from my holiday and can update everyone on the Vignette information.
• The rental car's license plate number and country are required to buy one so it can't be purchased before leaving home.
• They are easily bought in person at several authorized gas stations listed on the DARS website. These include gas stations in Croatia. There's no need to purchase online unless that's your preference.
• As well, they are always sold at the first gas station after the border crossing when entering Slovenia.
• If you buy the Vignette before entering Slovenia, have the attendant post-date the Vignette to start on your entry day, when they enter the information on the DARS website for you. We bought ours at an authorized gas station in Rovinj, Croatia a few days before entering Slovenia and the attendant was very familiar with how to post-date it.
• Buying a Vignette at the gas station was a simple process that took about 5 minutes. I showed the attendant a photo of our car's license plate rather than just saying it to him, so that we could make sure everything was correct. The toll cameras in Slovenia do a license plate match and if it's wrong, you may be dealing with a hefty fine. And there's no way, driving down the toll highways, to know if you got it right.
• When you return home, keep your receipt with the license plate and dates of the Vignette for reference in case you suddenly get a fine in the mail and need to prove you had the Vignette.
Also, the border crossings were all very quick going into and out of Slovenia. There were no lineups. We basically slowed down as we approached and were waved through.