I have the following data as shown in the image. I want to make sure that the username field is unique. How can I enforce that? Bear in mind that my document id is already unique and I don't want to use my username as the document ID

There is no way to enforce unique values of fields in Firestore. The only uniqueness you can guarantee is the document IDs within a collection, so the solution is to create a new collection where the user names are used as document IDs.
This has been discussed a few times before, so I recommend checking out:
If you love us? You can donate to us via Paypal or buy me a coffee so we can maintain and grow! Thank you!
Donate Us With