The definitions between on- and off-shell are given in Wikipedia.
Why is it so important in QFT to distinguish these two notions ?
It's important to distinguish them because on-shell and off-shell are opposite to each other, in a sense. On-shell describes fields that obey the equations of motion and real particles; off-shell describes fields that don't have to obey the equations of motion and virtual particles.
On-shell are momenta with $p^2=m^2$ with the right $m^2$ for the given field; off-shell are momenta that don't obey the condition.
Amplitudes with external particles that are on-shell, i.e. on-shell amplitudes, express the scattering amplitudes and may be directly used to calculate cross sections etc. Off-shell amplitudes i.e. amplitudes with external off-shell momenta encode much more general correlators.
In some theories, i.e. quantum gravity i.e. string theory in the flat space, only on-shell amplitudes for the external particles such as gravitons may be calculated. On the contrary, the analogous quantities to these on-shell amplitudes in the AdS space may be expressed by off-shell correlators in the corresponding CFT.
It's always important to know whether the 4-momenta etc. we are attaching are obliged to be on-shell or not, i.e. whether they're on-shell or off-shell. If we substitute off-shell momenta to on-shell-only formulae, we get meaningless or ill-defined results. If we only substitute on-shell momenta to off-shell formulae, we miss a significant portion of the physical information.
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