I would assume RFID would be more accurate to begin with. Seems like there's a lot of room for errors with their proposed technology.
BUT what if their goal isn't to make razor thin margins at grocery stores, but to test out their tech on human tracking. You've got to believe that they have a more long term plan than making a better self-checkout.
They can now tie in your Amazon Go app with you as a person. Most likely all the sensors and cameras in the store will be both tracking you via your app with Bluetooth, but also perhaps body heat sensors and the like that track you based on your unique body pattern.
Then they can tie this in with your Amazon Prime account to better improve recommended purchases to you, they can tie this in with your Prime Now account and your home address and more immediate delivery needs. Drones, Kindle, Echo as well.
The goal is deeper analytics and tracking on individual humans. That's how Facebook makes their money, and Amazon can perhaps have deeper data on individuals than any other company tracking browser cookies.