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OK so in settings you have added the NAS and are still getting no storage present?
If so can you get into the files on your NAS and see if you can delete the .wdtv file (the full stop . is correct as it is a hidden file) you need to get your PC to show hidden files.
This has worked for me before, however I do not use a NAS anymore.
Try network server on WDTV instead of media server you should be able to browse the NAS folders directly. Synologys media server (DLNA) is known to behave weirdly with auto discovery, the DLNA server configuration can become corrupted.
There is a process to reset the DLNA server if you look over on Synology forums but it involves a some technical work, you could contact synology tech support and ask for their help or switch to another media server on the NAS like Serviio for instance.