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...
I'd rather have it run on the lower voltage - generally easier to step down than buck up. Either way, the modules are pretty cheap, small, and easy to find.
The regulator can take that, but as far as I can see it's only for DVDD, the core voltage of 1.1 V. You also need at least IOVDD, which should be between 1.8 V and 3.3 V. So you'll need to supply some lower voltage externally anyway.
I suppose the main draw of the regulator is that the DVDD rail will consume the most power. 1.1 V is also much more exotic than 3.3 V.