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this may help to see if connecting direct to modem works
Silly question, you are with BT and not Plusnet aren't you?
Second silly question, are you sure you are not entering email@example.com
BT username and password are firstname.lastname@example.org and bt.
Edit: Third silly question are you configuring the devices as PPPoE and not PPPoA.
Remove your Homehub/router from the equation.
Use the Openreach modem and set up a direct connection from your PC to the modem which will eliminate the Homehub or any router. Follow this guide to do that. Use your computer as normal to see if it connects. If it does connect you will know it is the router that is causing your problem. If you can not get a connection you will know it is the modem that is the problem.
Step 1: Connect the Openreach modem to the socket.
Step2: Connect your pc/laptop into the modem using LAN1 port
Step3: Open network and sharing centre on Windows and click set up a new connection or network
Step4: Connect to the Internet then click make a new connection Broadband PPPoE
Step5: Username email@example.com and the password as BT
Step6: connect, If it doesn't,keep pressing try again until it does.
Just to clarify,
What Homehub are/were you using?
Are you on VDSL or ADSL?