The stuff emits alpha radiation (i.e. a helium-4 nucleus) - not too dangerous outside the body, as it has only a range of a few cm and is almost completely blocked by a sheet of paper. If it's taken in though, it's a different matter: alpha radiation, with a charge of +2, ionises (removes electrons from atoms) strongly, altering body chemistry. According to that bastion of knowledge, Wikipedia, half a gram of polonium -210 can release enough energy in its decay to raise its temperature over 750 K ( subtract 273 for T in degrees C). 1g of it can produce 140W of power.
Even better - well, not if its inside you - Po-210 has a half-life of around 138 days. I guess that means that if you inhale 2g of it, you'll end up with 1g of it still in you after more than 3 months. And half a gram, you'll remember, is pretty powerful.
In any case, despite being a truly horrific case of brutality and inhumanity, it seems to be a classic thriller played out in real life; science and politics mixed up in just the right amounts. I guess we're gripped by it for the same reason that we watch CSI.