Some uses for multiple radios include:
-You can monitor one thing one one radio, another channel on another radio, etc. With one scanning receiver, you may miss transmissions on one channel while your radio has stopped on another channel.
-Different radios have their strong and weak points. Some may be better for a particular band, others may have better scan functions. And others may have better audio, while others may be more rugged. You can mix and match different brands and models to optimize on each particular radios' strong points.
-And yet still, some folks aquire many different pieces to build a collection, much as any of us collect any other items that interest us. ie. model trains, baseball bats, stamps, bottle caps. Some radios may have a bit of nostalgia; maybe a radio that the owner used as a child, or in previous employment. You only have one head, yet many guys have a bunch of caps. Whatever fits your "mood" so to say.
As for multiple radios in a vehicle, the same holds true for hams and the hobby types. In a professional setting (Law, Fire, etc),maybe they are equipped to communicate with neighboring juridictions or towns.
And dont forget, most commercial/government grade radios come in one frequency range, unlike scanners. So multiple radios allow them to communicate on various systems and frequncies.
Hope that helps.
Rich