I have the 3A version of this (PPS3203T-3S). One of the major reasons I bought it was for the serial programmability, and as Dave noticed, that doesn't work at all. The download for the 3203 was a broken link, and the 3205's software just didn't work.
It looks like somebody sat down with some VB or similar GUI design tool, dropped in some windows, and shipped that. I'm not even kidding: I ran this in a VM, selected the serial-USB port and told it to connect while sniffing USB traffic going through the VM. It doesn't touch the serial port at all; not a single USB packet. FWIW I do this all the time on that VM; the method works, the software does nothing.
I sent a mail to Atten, but received no reply of course. Not that I was expecting anything there. The distributor where I got it (TME) also declined to reply. It looks to me like Atten simply did not implement the programmability feature, but is still selling it that way. Very, very questionable.
I had a look inside. The separate serial board goes to an MCU board, centered around a chip labelled STC 89C58RD+. A quick google turned up a datasheet that contains a few package outlines and no text whatsoever. Good luck getting it to work by reverse engineering that.
I didn't actually get a sheet with serial commands with the unit, only the manual. Dave, any chance you could post this? I'd really like to see if it's at least implemented in the firmware.