Did you configure the application to use a drive letter for the NAS or a UNC path (\Servername\Share)? Use a UNC path in case the drive letter is not being mapped.
Open task manager and find the program in the details tab. Verify that it is running as the user account.
Does the NAS have the equivalent of a security eventlog? Do you see logon errors when the service is started?
Run Process Monitor from http:\www.sysinternals.com and see if you can find any file I/O or network traffic to the NAS. See any errors?
The drives are mapped using UNC paths.
Within task manager the app is running as my local user correctly.
The NAS event log shows one connection event as successful with the comment " User from [desktop] via [CIFS(SMB3)] accessed share folder". I believe this is the event when I sign into windows, as I've mapped the drive with credentials to automatically log in. So there should be other access events, right? (I'm actually running two similar applications that both should be accessing the NAS). I've stopped the service and restarted it and see no access attempts within the NAS logs.
I'm a little lost on what I should be looking for with the Process Monitor. I've stopped the Service, cleared the log, then restarted the Service. I see network traffic, but my NAS's local IP address does not appear.