You seem far more experienced in the subject than I am so I'll take your word for it.
I'm a security engineer for Riot. This is literally my job. :P
was that 2FA (which was and still is far more available than MFA (which is mostly used by banks as far as I'm aware?)
2FA is a subset of MFA. Many websites these days use a form of MFA where they check both the IP addresses you're logging onto as well as the TOTP prompt. If you have any website which prompts you if youre "logging on from a different location", they are using MFA. I say the term MFA rather than 2FA because 2FA specifically refers to two factors, where MFA gives you more room.
was by far the most effective way to secure your accounts.
As mentioned previously, while MFA is a great way to secure your accounts, it does nothing for you unless the attacker has already guessed your password. It's a protection of last resort should all other protections be exhausted. You should still use it where possible, but if your password is already very secure then there's a good chance you're fine. In general, if you have a unique password, you're much more likely to lose your account to a social engineering attack than someone guessing your password (this is true for anything, not just League).
Even more so than a password manager
This should be covered in the above section, but TL;DR MFA is an extra layer of security on top of a secure password, it should be done in addition to instead of being a security measure in its own right. Defense in depth, yo.
do remember being told that there was supposedly a nearly uncrackable form of protection in the works that was at the time only used by some militaries.
The thing about cryptography is that in general an algorithm is less secure if it is secret. "Military grade encryption" is mostly a thing of the past, with the same encryption used by militaries being used by civilians and private corporations. I very much doubt there is any form of 'uncrackable' protection, particularly if we're using passwords - There is no way to make a passphrase based system uncrackable, since someone can still always guess the password.
It just baffled me how many people in this thread were completely against the idea of *optional *stronger protection for their accounts.
Security benefits do not come in a vacuum. Poorly implemented MFA may increase security (it may not) at the expense of a guaranteed decrease in personal privacy. They also come at a cost of ease of use - If we had a system where you had to log into your email every time you logged into the game, that would be really annoying, especially if the client crashed in the middle of a game, for example.