I am confused by your question. First you say you want to remove a subscription from your account, then you describe a scenario which instead indicates you are trying to possibly remove a payment method. Which is it?
This support article explains how to cancel a subscription from Apple on an Apple mobile device, Mac, PC, and online (see the Android section) ➔ If you want to cancel a subscription from Apple - Apple Support
You cannot remove the only payment method (account balance does not count as a payment method in this scenario) if you have an active subscription. "Active" means even one that you have canceled but has not yet expired fully. You can only update a payment method in this scenario and a new one has to be added first before removing the old one.
See this article for information about updating payment methods on various platforms (iPhone, Mac, etc.): If you need to change or update your Apple Account payment method - Apple Support