Well, if I understand correctly, that should be easy.
First, copy the existing Files view to a new view and rename it. You don't want to edit or delete the original view until you are happy with your new view. You may want to keep the original anyway. You can drag and drop the Files view to the Video level in the Navigation Tree to copy it, or use Ctrl-C and Ctrl-V to copy and paste.
Now right click on the new view and select Customise View.
Click the "Location" Category on the left and click Edit.
Browse to the \\Network Store\Media Files\ location on your file system and select that (or just copy and paste that location in), then OK, OK, out of there. You will see a warning about editing a Locked View. Just accept the changes. You could also unlock the view under the Advanced settings on the right.
Done.
Check out the new view. Does it do what you want?
You should try to read up about views a bit more though, as you can probably produce a better custom view than simply using the directory structure. But if it works for you, great.