This is my second attempt at posting this. The first post disappeared into the Garmin ether, so good luck to this one!
(It didn't, it was awaiting moderation but I've now deleted it as you posted again…
I've been having the same problem. It's so frustrating that Garmin know about these slack design issues but don't even update the help pages or respond to forum/support questions and rely on the "community" to ad-hoc resolve every trick technical thing like this. Very poor support and it really should be a simple fix for anyone who knows what they're doing.
Anyway, back to the file linking - yes, this seems to work well but you need to remove the "/H' tag. You don't need a Hard Link, just a Symbolic (soft) works for this purpose and doesn't require consistency in the disk format type.
So, change,
mklink /H "C:\Users\username\Music\iTunes\iTunes Media Library.xml" "D:\Your_Custom_iTunes_Folder\iTunes Library.xm"
to
mklink "C:\Users\username\Music\iTunes\iTunes Media Library.xml" "D:\Your_Custom_iTunes_Folder\iTunes Music Library.xml"
Obviously you'll need to substitute in the file path and filename of the Medie/Music library - it seems that different versions of iTunes have different names for this xml file (Media Library, Music Library or just Library), so check in the default c:\ drive iTunes folder.
This so far is working for me and although it's a pain plugging in to get updates, it took only 20 seconds to transfer two podcasts which previously took the best part of a hour to suck up over wi-fi with one of the other Music "apps".
Seeing this old thread, I did some experimenting with the current Garmin Express 7.7.10 and managed to get the Music seen with it, even if the library and music files were stored on another partition and also another SSD - see post here: forums.garmin.com/.../1339035