(requires paid version of VLC Remote)
Unfortunately, VLC doesn’t recognise aliases or shortcuts (it just tries to play them), so these won’t help you.
There is a dedicated drive button in the browse page that will take you to your full drive list. If you are using Windows and don’t see your external drive, then you may need to make sure that your external drive is mapped to a drive letter.
You can even set your external drive as your default directory to make browsing faster in future. Just tap on the heart/folder icon when you are in the drive you want and that will become your default folder for when you next launch this remote.