Because the solvents and propellants are generally flammable, and often the binder is also flammable, especially in its fluid form. The binder is also sticky. Under pressure, some of these materials can be considered explosive, or nearly so. Most of the methods of “decanting” an aerosol can involve concentrating a portion of the liquid in a small container by venting it through a plastic tube. This cold, concentrated liquid contains the propellant, usually a flammable hydrocarbon that is a gas under atmospheric pressure, but has been condensed into a liquid before being put into the can. If it boils off slowly and there is no source of ignition at hand, well and good. If it boils off rapidly, on the other hand, there are plenty of sources of ignition—I doubt if the typical work area has flash-resistant electrical connections. There is also a slight chance of static discharge, especially in the winter months.
If it ignites while being decanted, you get a fireball, possibly with shrapnel. Two foot diameter for one of the pint-sized cans, 4 to 6 for the larger ones. Quite spectacular. No saving throw.
While the chances of ignition are small, burns are very painful and take a long time to heal. Insurance companies and fire marshals take a dim view of things like this, too.
Accidents are called accidents because they are unexpected and rare. How rare is up to you.
Assuming this operation is done in a proper spray booth, the release of potentially toxic materials into your breathing air is minimal.
As a final note, aerosol paints are formulated and designed to be sprayed from the valve and spray head on the can, not from an airbrush. Why not just use the stuff as it was designed? Less messy and much safer. The only good reason I’ve ever seen to decant an aerosol paint (other than in a lab for research purposes) was if you need just a small amount for touch up work. In that case, less than a second spray into the cap is safer and provides all the touch up paint you could possibly need.
In short, sure you can do it and get away with it. But why bother? If you want to take unnecessary risks, buy a lottery ticket. Then if something unexpected and rare happens, it will make you happy.