Will the balance showing in my account be automatically applied to any/all purchases?

Yes, but there are exceptions:

How App Store and iTunes Store purchases are billed. Click here --> https://support.apple.com/HT201359

"Which payment method is charged?

When you buy items or pay for subscriptions, Apple automatically attempts to charge your payment methods in this order:

1. Apple attempts to use your Apple ID balance to cover the full amount.

2. If you don't have Apple ID balance, you don't have enough to cover the full amount, or an item cannot be paid for with Apple ID balance, Apple attempts to charge your primary payment method (typically a credit or debit card, but varies according to country). The primary payment method is at the top of the list in Settings on your iPhone. You can control which payment method is at the top of the list.

3. If there's a problem with the primary payment method, or if the primary payment method can't be charged for the full remaining amount, Apple attempts to charge your other payment methods in order from top to bottom. If none of them can be charged, Apple may try again.

Some purchases aren’t charged to your Apple ID balance

- If you're in a Family Sharing group, purchases are charged to your personal Apple ID balance. If you don't have enough Apple ID balance to pay for the purchase, the remainder is charged to the family organizer's primary payment method.

- You can’t charge gifts to your Apple ID balance. If you send a gift or gift card, your primary payment method is charged.

- Some subscriptions might not be charged to your Apple ID balance.

Yes. Any balance will be automatically used for any purchase until it's completely depleted.