Yes, VCC Pin on the NAS is directly connected to the NAS's internal 3.3V Power supply and is an "output" therefore.
The NAS powers itself and Rx/Tx is directly connected to the CPU without any electronics.
So you have to be careful what you are doing for not destroying the chip.
Did you have a look at or the
MRT unbricking guide or our HowTos at our
NAS2000 Wiki where there is an article about
soldering a RS232 port to a NAS2000 (is different to your NAS but the basics are the same).
If the USB cable/adapter needs external power depends on its construction.
In your case it seems to need external 3.3V for supplying the PL2302 I/O buffer. With this voltage the output pin is driven and sets the input threshold.
(For other electronics it could also be 2.5 or 1.8V)
HWguru