Try to rename (or delete) the BSplayer.xml file located in
X:\Documents and Settings\USER_NAME\Application Data\BSplayer and then reopen BSplayer.
This way the settings are gone, but you will have a clean install of BSplayer and can try to change again the "Allow multiple instances" option.
Can you also tell us which settings have you tried in Media Library? (the right setting for your purposes is Play not Enqueue)
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