In my understanding, in flex fuel cars, it take a couple of minutes for the ECU to "understand" and adapt the mixture when changing from gas to E85 or vice versa. So it's always better, when changing the fuel completely, to do it when the car is hot and drive it for a couple of minutes. Olders cars can take more time to adjust, newer ones may be way more efficient, depending on how they identify the fuel they are running.
That being said, a flex fuel car should always start with any fuel (E85 or gas) regardless of the situation.
What was the temperature when you cold started it with E85? Ethanol is hard to start when cold, but again, flex fuel cars should have some systems to overcome this.
I live in Brazil, and you may know that we use ethanol in cars since the 80's. Flex fuel cars started in 2003, and before that we had cars that run only in gas or ethanol. We don't have E85, only E100.
I own both worlds, a neat ethanol car ( 94 Opel Kadett), and a flex fuel car (09 Honda Fit). The 94 has only 1 injector on a TBI style injection, it has a auxiliary gas tank (1L capacity) on the engine bay, that literaly squirts gas on the intake through a solenoid on cold starts. The idle is always sketchy when cold. The Fit also has the auxiliary gas tank, but with a much evolved system that has 4 injectors exclusively for the cold start with gas from the little tank. The idle in the Fit is always smooth.
Cold starts on ethanol is a challenge, but could pass unnoticed depending on how your system work and the ambient temperature. But i take my experience using E100, which should be better with E85.
You should check and understand how this "cold start system" work on your car, if it have any, years without using E85 may have left some parts of it not working properly.