I was kinda worried the interface to the ESP32 would have been like the origional ESP8266 where you used AT commands. But it looks like the Wifi library abstracts out whatever interface they're using for the ESP32, so I was at least happy to see that.
Since the ESP32 handles the USB interface, it's probably possible to program both microcontrollers. I can't imagine a practical use for that, but bet it gets done pretty quick.