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Once created if you browse in your Baldur's Gate folder, you will see Cache directory. It works the same way that a normal directory. Excepted anything done inside is in fact done to the real folder you chose as target with mklink.
(PS: The target folder must exist before using mklink)
To delete a Directory Junction, just delete the "fake" directory using the rmdir command.
You can also use the Windows Explorer to delete the "fake" directory, but then unlike with the rmdir command, it will also delete all the files contained in the real target directory.
Ref: MKLINK
About the UNC, Any custom "HyperOverride directory" must be placed inside the HyperOverride directory.
Example: C:\Program Files\Baldur's Gate\HyperOverride\MySpecialOverride
with such shortcut to launch the game: HOLoad -ho:MySpecialOverride
HOLoad only accepts the final directory and automatically prefixes it with "C:\Program Files\Baldur's Gate\HyperOverride\" (or wherever your BG is installed) to find the full path.
HOLoad does not accept a full path. So you cannot specify a full path whatever the form including UNC.
Note, that if you are really about splitting stuff on various HD, and using HyperOverride you can still use a Direction Junction for the HyperOverride folders as well if needed. I don't know why would someone resort to such configuration but since you are interested, just pointing it out
