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The prompt upon activation will display that you already own the product.
The other questions are irrelevant since you already have a license showing that you own the game on this account.
Here are my steps:
1. I uninstalled my current Steam (making sure to backup any custom ini tweaks I did etc.).
2. I reinstalled Steam in C:\Users\<me>\AppData\Local\Programs\Steam.
3. I created a new Windows account AND a new Steam account.
4. I installed Steam again in the same folder location but this time for my alt self.
4. I purchased XCOM 2 Collection Bundle using my alt Steam account.
Voila! Now both Steams and all games/mods/settings etc. are completely independent. Note that you will need two different e-mail accounts for yourself as well, and really the most viable when the game of interest has a great sale like XCOM 2 right now!