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So it just pulls files directly from the NAS and plays them like a PV would
Exactly.
And the Nvidia Shield CPU and RAM is better than what any cheap NAS would have. You have to get quite pricey on the NAS to get the equivalent. The remote playing, should you need that, would be fine on the Shield as the CPU supports hardware encoding meaning the CPU does the work rather than software, so it transcodes effortlessly.
There are limitations to the Shield... super large collections slow it down. But my 1,000 film collection was fine, it was only the 100,000 audio collection that really bogged it down (especially as Plex likes to fetch thumbnails for everything).
For a film and TV collection... or a small/medium audio collection... the Shield is awesome. Besides, it's an upgrade to whatever your smart TV is. And then if you want to be privacy conscious you can actually disconnect the TV from the network and just use the Shield for everything.
Ah yeah, I knew you were a fan of the shield. So it just pulls files directly from the NAS and plays them like a PV would. That does sound like a more sensible approach tbh.