Hi,
The documented prerequisite for being able to add additional MailFrom on your custom domain is to first increase your default email sending limit. This is what will enable the +Add button.
There is a way to add additional MailFrom via Azure CLI (example) / PowerShell (example) without first increasing your send limit, however, I recommend you go ahead and increase your send limit regardless.
Please carefully follow my instructions below to submit quota increase request and not get stuck in endless loop. The quota increase request is free.
Please let me know if you have any issue creating case in a comment below and I will assist further.
Please carefully follow instructions below to create a new Service and subscription limits (quotas) request to increase quota for Azure Communication Services.
1. Navigate to this link to start the process:
https://portal.azure.com/#create/Microsoft.Support
2. Enter quota in the box and click Go
3. Select Others / Service and subscription limits (quotas) and click Next
4. Click Create a support request button, as shown
5. Select Issue type: Service and subscription limits (quotas), Subscription: <subscription that needs quota increase>, Quota type: Azure Communication Services Email: Sending Limits, click Next
6. Open Notepad (or other text editor). Navigate to Email quota increase article, click Copy button in upper right to copy text, and Paste it into Notepad. Add your company info to the file and answer all questions, then save to a .txt file on your computer. You will need this file later.
7. On Additional details tab, click Enter details, select location, resource group, ACS Email domain resource, New Email sending limit you would like to request, confirm request by entering the tier enum (200, 225, 250, 275, 300, etc.) click Save and continue.
8. Still on Additional details tab, click the blue file folder icon, select the .txt file you created above, and click Open to upload it.
9. Finish filling out Additional details tab, click Next, review information and click Create. You should receive an automated email within a few minutes.
Please click Accept Answer and upvote if the above was helpful.
Thanks.
-TP