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if you only just upgraded, then it is most likely a windows 10 glitch or timeoout on network sharing.
i see this a lot - after upgrading all pcs in house & sorting all shareing settings & permissions I will often see w10 take a few seconds to look for a PC on the LAN, then come back with an error message saying " cannot access it", but then when I retry or run the troubleshooter it works after all.
it is intermittent and because retry always works I just live with it. it may be a w10 bug that shows only after sleep/wake or after non use of that network link for many hours
so I am guessing that in your fail case, calibre said let me write to the NAS & W10 said "huh - I can't see any NAS"
test by trying at random times to access that NAS via windows outside of calibre & see how well behaved the share is
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