I suspect you are somehow entering the password incorrectly.
You could try changing the password in webmail to see if that helps.
I have assumed your wife's emails are associated with your broadband account and aren't just her email accounts from a now non-existent broadband account.
Yes I created my wife's email accounts many years ago.
I can access my wife's email accounts using Blue Mail on my Samsung S10+ android phone (set up a long time ago). My wife can access her email accounts using Outlook on her Windows 10 PC.
Strange that my daughter couldn't access my wife's accounts using the Outlook app or Apple's mail app on my wife's new iPhone but the BT mail app could!
Are they shown in your MyBT under manage emails?
Yes both of my wife's emails are there