It can be used for AppleCare payments, but you cannot purchase AppleCare with it with the exception noted below.
What you can buy with your Apple Gift Card or Apple Account balance - Apple Support
The relevant portion here is:
For some recurring charges, like AppleCare+, you can't start your subscription with Apple Account balance. But as long as you keep another valid payment method on file and your Apple Account balance would cover an entire charge, your recurring charge will pull from your Apple Account balance.*
* In some countries and regions, your Apple Account balance can’t be used for some subscriptions like AppleCare+. Check if Apple Account balance in your country or region isn’t supported.