If your current ADSL router is already using PPPoE LLC, then 9 times out of 10, a Desktop PPPoE connection still works - by "passing" alongside the currently configured PPPoE connection that has been configured on your ADSL modem for everyone else on the network - noting that your Desktop's PPPoE connection does not interfere, other than compete for whatever DSL connection bandwidth you have, ie. the speed of your line.
Anyway, I set it up at home - all my PC's at home remain unchanged and use my default MWeb ADSL via the MWeb login that exists on my Modem, whereas on my Gaming PC I make use of the Alternate account via a PPPoE connection.
Here are the screenshots:

1. First Get Properties of the Network Places, so that I can choose
Set up a New Connection or Network

2. I choose the 1st option to connect to the Internet via a broadband, blah blah blah

3. It tells me I'm already connected (via the Modem already having config and connected to the Internet), I can simply ignore this can continue

4. How do I want to connect? With Bananaz and Jam, no wait, Broadband PPPoE.

5. Put in the username and password and click connect. (Don't do this while you are downloading, the new connection becomes the default)

6. This what I see when I go back to step one after finishing the config and choosing
Change Adapter Settings
from the left hand panel - to see my Ethernet Adapter and my new PPPoE adapter

7. The screen you will see when you double click the PPPoE adapter you just set up.
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