Hello Frederickfox,
Thank you for using Apple Support Communities! I understand that you're unable to add your debit card to Wallet, and you'd like to use it to pay for an iCloud storage plan. I would be happy to help provide more information about this process.
When you upgrade your iCloud storage plan, the payment method that you have on file for your Apple ID is what would be charged for the subscription. This is different from the payment methods you have under Settings > Wallet & Apple Pay. Certain countries or regions may not accept debit cards as a form of payment for your Apple ID.
I suggest first ensuring that upgrading to a larger iCloud storage plan is supported in your country or region:
iCloud storage plans and pricing - Apple Support
After that, follow the resource below to add the debit card as a payment method for your Apple ID:
Payment methods that you can use with your Apple ID - Apple Support
If you're unable to add this specific card following those steps, you'll want to contact your financial institution for more information. If you're able to add the card OK, upgrading your iCloud storage plan should then charge this card:
Manage your iCloud storage - Apple Support
Take care.