The starting location has no effect to libraries.
Instead you should add the path, where your libraries are, to
Application Preferences -> Paths setting.
Presumably you have to restart LibreCAD to apply this setting, but then all sub folders, containing DXF files, should be listed in the Library Browser.
see also
https://forum.librecad.org/Blocks-External-Library-tp5716343p5716346.html
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