Why is STP mol/liter so specific?
How do we know that one mole of an ideal gas occupies (exactly) 22.4 litres?


It doesn't.

The current recommended value for the molar volume of an ideal gas at a temperature of $T=273.15\ \mathrm K$ and a pressure of $101.325\ \mathrm{kPa}$ is $V_\mathrm m=22.413962(13)\times10^{-3}\ \mathrm{m^3\ mol^{-1}}$ (source). Note the given uncertainty; i.e. it is an experimental value  that is not exact.

Also note that these conditions do not correspond to STP. According to current IUPAC recommendations, STP corresponds to a temperature of $T=273.15\ \mathrm K$ and a pressure of $100\ \mathrm{kPa}=1\ \mathrm{bar}$. At this state, the molar volume of an ideal gas actually is $V_\mathrm m=22.710947(13)\times10^{-3}\ \mathrm{m^3\ mol^{-1}}$ (source).