If I start a Family Group, how can I make sure that they pay for their own purchases and not me. What settings do I have to use?

The payment method for Family Sharing is automatic:

1. If anybody in the family buys or subscribes to something, Apple first attempts to charge the item to that individual's Apple ID balance, if any.

2. If a family member does not have enough personal balance, any excess will be charged to the Family Organizer's primary payment method (usually a card of some kind). The Organizer's personal balance will not be used for purchases made by other family members. If it cannot bill the primary payment method then it will just work its way down the Organizer's list of payment methods until it finds one it can.

- "Some purchases, including gifts, can't be billed to Apple ID balance and will be charged to the family organizer's payment method." "Some subscriptions might not be charged to Apple ID balance."

Ref:

- Family purchases and payments - https://support.apple.com/HT201079

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

- Check your Apple ID balance - https://support.apple.com/HT202359

The only way you can enforce this is by going to them and saying, "Next time pay for you things yourself with gift card balance or I'll remove you from the Family Sharing group."