If you take an isolated hydrogen atom it will settle into the ground state with the spins opposed and stay there for ever. Not very exciting.
However if you take a hydrogen gas and you heat it, e.g. by shining starlight on it, then the hydrogen atoms will start buzzing around and colliding with each other, and every now and then when two hydrogen atoms collide one or both of them will be jolted into the excited state with the spins aligned. The excited hydrogen atom will then relax to the ground state and emit a photon with a wavelength of 21cm.
So a hot hydrogen gas emits light at the 21cm wavelength. If you look at the light from the hot gas with a spectrometer you'll see a bright line at 21cm (well, it's not an optical wavelength so your detector does the "seeing").
Now suppose you take a cold hydrogen gas. This won't be emitting light with the 21cm wavelength but it will absorb 21cm light by exciting ground state hydrogen atoms to the excited state. The excited atoms will relax, but the re-emitted light may be in a different direction, or the excited atoms may lose energy by colliding with other hydrogen atoms and not re-emit the light at all.
So if a broad range of wavelengths passes through a cold hydrogen gas the 21cm light will be absorbed. If you look at the light from the cold gas with a spectrometer you'll see a dark line at 21cm.
It's not my area, but I think in practice the temperature required to produce the emission is so low that we only ever see emission at 21cm and never absorption.
The 21cm is the wavelength, $\lambda$, of the electromagnetic radiation. The frequency, $\nu$, is given by:
$$ \nu = \frac{c}{\lambda} \approx 1.42\text{GHz} $$
For comparison, microwave ovens produce electromagnetic radiation with a frequency of 2.45GHz.