Hey @jsehwani , @ChuckPa
Were you able to get this working? I had a similar issue and I’ll detail my issue, root cause, and solution.
Issue
Plex would randomly stop grabbing metadata. It would start working, and then stop at intermittent times. The odd time after starting and stopping PMS, the metadata would end up pulling, but it wasn’t a guaranteed solution.
Troubleshooting
While viewing the PMS logs in real-time, I noticed after trying to refresh metadata for an object, I would see Error issuing curl_easy_perform(handle): 28. That was telling me there was a timeout trying to grab the metadata.
I did something similar to what @sa2000 suggested in this post and ran wget http://image.tmdb.org/t/p/original/lxvTtIQOGbi7ZLpyCCEMGAinvz5.jpg on my DS918+.
Output:
--2018-12-17 03:11:49-- http://image.tmdb.org/t/p/original/lxvTtIQOGbi7ZLpyCCEMGAinvz5.jpg Resolving image.tmdb.org (image.tmdb.org)... 2606:4700::6810:399b, 2606:4700::6810:3c9b, 2606:4700::6810:3a9b, ... Connecting to image.tmdb.org (image.tmdb.org)|2606:4700::6810:399b|:80...
This was odd. I know I had disabled IPv6 in PMS under Settings -> Network by unchecking the Enable server support for IPv6 checkbox early on during my setup process. 
My Root Cause
I believe the issue was happening for me when the DNS results for tmdb.org were returned and cached with the IPv6 address. That cache would stay there for days (potentially) until it expired and sometimes I would get lucky with the IPv4 response caching instead and then metadata refresh would work as expected.
My Solution
In the Synology DSM web portal, navigate to Control Panel -> Network -> Network Interface , select the for your network and click Edit (in my case, my interface was LAN 1). Click the IPv6 tab and change IPv6 setup from Auto to Off and reboot the Synology NAS.
After reboot I SSH’d back in and attempted to grab the same file from tmdb.org.
Output:
--2018-12-17 03:16:03-- http://image.tmdb.org/t/p/original/lxvTtIQOGbi7ZLpyCCEMGAinvz5.jpg Resolving image.tmdb.org (image.tmdb.org)... 104.16.61.155, 104.16.58.155, 104.16.60.155, ... Connecting to image.tmdb.org (image.tmdb.org)|104.16.61.155|:80... connected. HTTP request sent, awaiting response... 200 OK Length: 61320 (60K) [image/jpeg] Saving to: 'lxvTtIQOGbi7ZLpyCCEMGAinvz5.jpg'
Now since the IPv6 stack is completely disabled on the Synology NAS, the traffic is forced through IPv4 and resolves properly.
TL;DR
Try disabling IPv6 on your NAS and see if that fixes things.
Hope this info helps.
Cheers!