To move a database file, use this command:
ALTER DATABASE yourdb (NAME = '<logicalname>', FILENAME = '<newpath>)
Where logicalname is what you see in the first column in the output from sp_helpdb and newpath is where you want the file to be located.
SQL Server will not move the file for you, but you need to stop LocalDB and then move the files yourself. Then start LocalDB again.
To set the default directories, connect to the server in Object Explorer in SSMS, right-click the server itself and select properties. Go to the Database Settings page:
I will need to add the disclaimer that I have not verified that this actually works for LocalDB.