Follow the steps found here to add a custom RPC network:
Then follow the steps found here for the custom network settings:
https://www.xdaichain.com/for-users/wallets/metamask/metamask-setup
Specifically:
Network Name: xDai
New RPC URL: https://rpc.xdaichain.com/
Chain ID: 0x64 (100)
Symbol: xDai
Block Explorer URL: https://blockscout.com/poa/xdai