Bluezip,
I think your reply above was victim of the dreadful WHF forum software.
The PS audio DAC uses DLNA to access the NAS, DLNA in turn uses TCP which is a lossless async protocol. Unless your old cat5e cable was knackered, there is no way it wouldn't have coped with the relatively low bitrate required for audio.
So, if it isn't the data making a difference, what else? PS audio make a big deal about their fancy clock, so it can't be anything to do with timing - and TCP is async anyway.
Your powerline extender is however the work of the devil, squirting who knows what RF down the mains cable. Perhaps your old cat5 cable was acting as an aerial and your PS audio box has sub-standard filtering? Absent suggestion bias (which I am pretty sure is the answer), try throwing the powerline extender away and see if that makes any difference.