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Experimenting with VMs is the way forward.
Basic networking knowledge is vital. And being able to configure your own firewall(s) safely is an important skill. Check out something like Foomuuri, or Firewald. Shorewall is brilliant for documentation and description of issues (with diagrams!) but it does not use the newer Linux kernel nftables and is no longer actively developed.
Go for it with Nextcloud.
I would also recommend at least having a shot at setting up an email server, although I would recommend pushing through to a fully working system. It is possible, and is very satisfying to have in place. The process of setting one up touches so many different parts of internet function and culture that it is worth it even if you don’t end up with a production system. The Workaround.org ISPMail stuff is a good starting point, and includes some helpful background information at every stage, enough so you can begin to understand what’s going on in the background and why certain choices are being made - even if you disagree with the decisions.
Python is great for server admin, although most server config and startup shutdown snippets are written in BASH. You will no doubt have already begun picking that up as you interact with your VMs.
Naomi Brockwell https://www.nbtv.media/episodes does a good job of blending accessible presentation of privacy issues with technically viable solutions. Recently she’s been more on an advocacy tack, but there are some gems in the back catalogue that explain not just why you should care but the sorts of products/software you can use to address your concerns. She provides suggestions, but you should take those as just an idea and develop your own answers!
So, in between watching those videos find out all you can about how Debian (for servers) and OpenWRT (for routers) work from their websites, and use $preferred_search_engine to learn about why Proxmox, Unbound, Postfix, Dovecot, XMMS, WireGuard, Nextcloud can help improve your privacy.
Get that used Optiplex, install a Linux on it and begin experimenting! Don’t worry about the perfect hardware config yet. You can source other parts if you feel you really need them later. Although more RAM is always good, but you knew that already.
Along the way you will want to learn enough to decide whether you prefer VMs or Containers, or a blend; which filesystem(s) you prefer; which distributions you are going to deploy; which backup system you are going to implement; whether Apache or Nginx; and whether you like systemd or want to simply blast off and nuke it from orbit. You may also want to take a look at Ansible now. And Git. Git has saved my server config bacon more times than I care to remember.
Not sure quite where to recommend you look for bang up to date introduction to Linux networking stuff these days. The Linux Networking Howto was hopelessly out of date ten years ago. The distribution howtos are pretty good on at least the basics. Wikipedia might be useful on more advanced topics. And then searching for specific problems or needs normally turns up some learned responses on stackexchange or equivalent.
And as one 90s kid to another, if you haven’t read Permanent Record by Edward Snowden yet, consider getting a copy. He grew up at the same time and does a great job of explaining why this journey matters.