Sorry, but I am full of questions today. I was just looking at My Account to check that all 5 of my TT email addresses were showing, and they are. But noticed there is a line for a 6th email address titled 'My Account email address' (see pic below). This appears to be available to me so wonder if it can be used or what it is meant for ?
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The MyAccount email address is for the MyAccount sign in using an email address not listed in your MyAccount, usually a non-TalkTalk email address, as the MyAccount username.
Currently you have a talktalk.net email address selected as the MyAccount sign in username. If you select the Setup link you'll be able to enter a different username.
Managing your email in My Account explains in the section Change your MyAccount username. There is a slight error in that description as it says select Edit - but if you select Setup then follow the details in the pop-up panel and select Submit to use an alternate email address for the MyAccount username.