Emission and absorption of photons from an electron is described by
quantum electrodynamics, called QED for short. This is an example of a quantum field theory and to properly describe the transitions in hydrogen would require a lot of background and technology. But we can get some qualitative information out using some information that requires a bit of quantum mechanics knowledge and some intuition.
Basically, the important idea is that the strength of the electromagnetic interaction is proportional to the electric charge, ##e##. The amplitude for a single photon transition is then proportional to ##e##, so the probability of a single photon transition is proportional to ##e^2##. Since the value of the electric charge depends on the system of units that we use, it turns out to be a much simpler to express this in terms of the dimensionless fine structure constant
$$\alpha = \frac{e^2}{4\pi \epsilon_0 \hbar c} \sim \frac{1}{137}.$$
So we can as well say that the probability for the emission of a single photon carries a factor of ##\alpha##.
Now suppose there is a particular transition from n=5 to n=1 that satisfies the angular momentum selection rules that Jolb pointed out. This transition can indeed proceed by the emission of 2 photons, but the probability of this happening is now proportional to ##\alpha^2##, so it is roughly 100 times less likely than the single photon transition. Similarly, the probability for the 3 photon transition will be proportional to ##\alpha^3##, so it is 10000 times less likely than the single photon transition.
Multiphoton transitions have indeed been observed and in fact allow certain transitions that are forbidden from occurring via a single photon transition by the selection rules. An important example is the 2s to 1s transition in hydrogen.