You're right, after re-reading the Power section on the datasheet it seems connecting 5V to the VREG_VIN should suffice to power the digital domains, but if you want to use the ADC, you still need a external 3.3V source.
The chip needs a) 1.1V to power the cores, b) 1.8V-3.3V to power IO, and c) 3.3V to properly operate USB and ADC.
The chip has one onboard voltage regulator, which can operate from 2.7V-5.5V. Usually it'll be used to output 1.1V for the cores, but it can be used to output anything from 0.55V to 3.3V. The regulator requires a 3.3V reference input to operate properly.
So yeah, you could feed the regulator with 4-5V, but you're still going to need an external 5V->3.3V converter to make the chip actually operate...