Brian, this is not a straightforward question to answer.
The barrier to a simple yes or no is that you have no idea if you are comparing identical items with the only difference being the transmission method or carrier.
The fact is that what appears to be exactly the same on , say, Qobuz and on your NAS may not be. The obvious thing to exclude are rips from CD. What is on the Qobuz servers are digital files sent to them by the record companies or perhaps from the studio where the master is kept after an order from the record company. Or by some other service provider to the record company. Whatever the supply chain there will not have been a CD involved. And CDs do not normally sound exactly like the production master even if they are supposed to.
All digital copies are supposed to sound the same. Do they? No. Try ( as I have) two CDs of exactly the same album, one from the USA the other from Europe. Chances are that they will have been manufactured ( including glass master preparation) at different factories with different equipment ( with different jitter profiles) and , very importantly, different house rules as to how they master ( for example the factory may normally only master to XdB maximum dynamic range ). They may sound different.
Similar things can relate to the digital files. There may be a supply to Qobuz by, say, Sony Music France as opposed to the file of the same album which was supplied to Presto Classical by Sony Music UK ( and which you have downloaded to your NAS).
There are many other slips between cup and lip to be aware of like remasterings ( some publicised, some not) where one version is on Qobuz and the other on your NAS but they appear from the artwork and metadata to be identical.
So, is there any sort of answer? Only very generalised. Broadly speaking my feeling ( no more than that) is that playing from my NAS is marginally better then from Qobuz. But as the difference is so slight another listener may choose the reverse as preferable.
BTW while writing this I have been listening to the “same” 24/96 album from Qobuz and from my download of it purchased from Presto Classical. The download sounds a little richer, the streamed version perhaps a little more transparent. Which is better?
Basically what I listen to from my NAS is my legacy collection. I use Qobuz to listen to new music either newly released or just not familiar to me. Some pieces I will return to on Qobuz but not purchase for various reasons. If , however, the piece is important enough to me then I will buy a download and add it to my legacy collection on the NAS.