I'm going to assume that this is a B-flat NON-compensating instrument, and that it features typical intonation characteristics.
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If you are willing to manipulate your upper #1 slide on the fly...
(which might include taking it to a qualified shop that can perfectly align that slide, as well as venting the #1 valve)
...since your four valve tuba is very likely not compensating, you're not going to get much good out of that 4th valve unless you continue to play C below the staff - along the very low F - with the valve combination 1-3, and do so with the first slide pulled out quite far (specifically for those two pitches).
Warm up your instrument and tune your fourth valve slide (or slides plural) until the valve combination 2-4 is just about in tune for B natural below the staff and very low E natural.
With many instruments, you might need to push the 1st valve slide all the way in for second space C natural (the same as with many 3-valve B flat tubas), and possibly for second line B natural as well. (Yes, this slide manipulation I'm referring to is "on the fly", so that slide needs to work very smoothly and easily.)
With your 4th valve slides pulled out far enough to tune the 2-4 valve combinations flat enough for good pitch, you then probably have enough tubing to play the very low E flat with 1-4, and probably helping it a little bit by pulling the first slide out as well.
If you really want to play low, you might end up with a good low D natural with the valve combination 2-3-4, but - with the setup that I've recommended - you might need to push the fourth slide in for that very low D (or not, depending on your playing and your instrument).
I'm not going to comment on pitches lower than that, because that's just sort of screwing around - even though practicing playing pitches lower than that improves the quality of sound of the low pitches which you are actually requested to play in written music.
I'm only answering questions related to tuning, because that's really the point of acquiring an instrument with more valves (more - and hopefully more desirable - tuning options).
My advice above isn't what most people do, but it's the best advice that I can give you - in my opinion. If you tune the fourth valve to play C & low F, your B natural and your low E natural are still going to be stinky sharp (in other words, several inches shy of enough tubing to play those pitches flat enough)... and that's after spending the money for a four valve instrument...so continue to play C & F with the valve combination 1-3, but pull the first slide out quite far so that those are now in tune.
Also, since this advice won't line up with very many other people's advice, expect subsequent posts to feature "yeah but with my tuba..." contradictions to what I've advised.
If you happen to have purchased a Miraphone model 186 B flat tuba, my experience is that there isn't enough 4th valve slide adjustment built into those to play B natural and low E natural flat enough with the valve combination 2-4. Only very early 1960s versions of that model featured a "loop-over" slide setup that offered enough tubing to do that. My suspicion is that they quit building the 4th slide that way, because Americans (not really understanding the logic of the system) complained that they could not play C and low F up to pitch with the 4th slide built longer like that.
