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Let's say I've got an Armor on one of my characters as well as Defensive Configuration, giving me an extra empty Armor slot. I then play Hunker Down which checks to see if I have an Armor or not. Since Configuration will be giving me an empty Armor slot, would I be able to put an Armor on my character through Hunker, or will it not work since I do still have an Armor in the 1st Armor slot?

It will not work since your Tank already has an Armor attached.
Source: Wizards of the Coast (2019-11-22)    【Link to Ruling】
Tags: Hunker Down, Defensive Configuration