A "cook-off" is just simply a round getting so hot that it explodes. Usually it's not extremely dangerous. When a cartridge is chambered in a firearm and fired, all that pressure generated launches the bullet from the barrel. That's the only path it can take, therefore it's concentrated enough to send the projectile flying at great speed while the barrel stabilizes it. When a round is just lying out in the open and is set off, it doesn't have any of those things to support it and the energy generated from the explosion is able to disperse all around it as opposed to being forced in one direction. That's why the bullet doesn't just take off as if fired from a rifle.
I am a fireman and one time I was at a fire where many, many rounds were cooking off. A 30-30 casing came through a window about 2 feet from my head and landed about 30 feet away in the street. While it likely wasn't moving at great velocity, I still would not have wanted to been hit by it. So if you have a fire, keep a safe distance from the home and alert the firemen about the ammo as you arrive. They will likely appreciate your info even if it isn't technically all that dangerous. And if they know where it is they might even be able to cool it down with a stream of water if the home is already fully engulfed and un-savable. Again, not really all that dangerous but it would pay to keep a safe distance just in case. I have been working many fires with ammo cooking off and that one experience is the only unusual thing I have had happen.
-Charging Handle