Ok, pardon my ignorance but I have a last question:
Will I need to reinstall the softwares/apps that I use, in XFCE? and more importantly, Can I use Gnome Boxes in XFCE desktop?
If you can pardon all of my ignorance's.
Ask all the questions that you need and never fear asking; Instead, fear what can happen by not asking.
No, your installed applications all remain the same. The only difference is the environment in which you use them, not in your access to them. All Gnome settings are also saved. So whether you log in on Gnome or on XFCE, you will find things just as you left them.
It is not the same as installing a dual boot or installing an operating system. Merely installing another WorkBench within which to perform your tasks. All yuor tools are still there.
Yes, and I do that, too.
Most applications will work in either Desktop Environment. You will find that there are some few applications that are set to be Desktop Environment dependent out of necessity; For example ZorinMenuLite or WhiskerMenu will only open and run in XFCE due to them needing the xfce4-panel. OR a Gnome-Shell only application, like certain Gnome-Extensions will only run on Gnome.
This really is not an issue since gnome-extensions exist to replace functionality that was removed from Gnome, but is Present as part of XFCE.
There is one gnome Extension that you may use that you would miss on XFCE: Zorin-Connect. It will not work, currently, on XFCE.
Fortunately, there is a Solution:
Install KDE-Connect.
sudo apt install kde-connect
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Believe me there were several times, where I regretted not asking questions. 
The questions you're asking are also bringing things up I forget to mention... I use and I install XFCE - to me it is something I am very practiced at. Which means that there is much I take for granted without realizing. Much that is familiar to me and I do not think of that is unfamiliar to someone else and they notice it like an octopus flying a biplane. By all means - ask.
Like KDE-Connect instead of Zorin-Connect; I forgot to mention that until you asked about which apps work and which may not.
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Once I follow your steps, XFCE will automatically be set as my default DE?
It will be default as long as it is what you Log In to on the Display Manager. Anytime you log into either desktop, it will defer to that the next time you log in - this is true for any DM, whether GDM, LightDM or SDDM... If you log in on XFCE and then do not log into Gnome after, it will default to XFCE each time. If you log in on Gnome for some reason, then just remember it will defer to that on next Log In. You can just log out, then back in using the Desktop Chooser at the upper right to log back into XFCE and keep on going from there.
For me, I log into Gnome sparingly and I rush back out of it. So, it always defers to XFCE for me because I never shut down the computer while logged in on Gnome.
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