I have never tried this but I do not know why this would not work.
In EFI Live there is a setting for fuel system. Under that is the configuration for the whole fuel system. This tells the system what size the main tank is and what to total fuel system capacity is.
So the main fuel tank size stays the same. The total capacity would change to main size + new tank size.
The Fuel Level Sensor Primary would also stay the same.
The Fuel Level Sensor Secondary would change, in the screen shown the tank size is 15 gallons. I would think you would set it all to 0 Volts. This would make the system think is empty.
A better plan would be to set it to use the level sensor in the new secondary tank. You would then need to do some testing. I would monitor the level sensor PID (GM.FUELLVLRS) with EFI Live as you slowly added fuel to the new secondary tank until it was full, taking notes on how many gallon at each level in the list. Connect the new tank to the factory transfer pump. In theory it should act as the original tank including the factory gas gauge.
After all that being said, who's going to be the guinea pig?