XML
<?xml version="1.0" encoding="utf-8" ?>
<sources>
<video>
<default pathversion="1"></default>
<source>
<name>TEST</name>
<path pathversion="1">smb://username:password@DISKSTATION/MEDIA/</path>
<allowsharing>true</allowsharing>
</source>
</video>
</sources>
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^ edit /storage/.kodi/userdata/sources.xml to use that format for the sources, it's fairly simple to crib the format. Change username/passsword and the name of the Synology and share names as you need them in each section (video/music/pictures/games/files). Save and reboot or restart Kodi to effect the changes. You cannot "browse" to add shares without downgrading the NAS to SMBv1 (not recommended) but this takes 5 mins effort to setup once and then you're done.