Yes, you could use radioactive material to generate heat. The problem is that your radioisotopes are generating dangerously high energy photons as they decay. So yeah, you could have a lump of plutonium sitting on your kitchen countertop, and you could boil water for your morning coffe with it. But it would be constantly generating gamma rays and xrays, and those would go zooming off into your kitchen and into your body. Not good.
Any source of radionuclides concentrated enough to generate a useful amount of heat is going to be much too dangerous to actually use.
However, note that lots of space probes use radioactive isotopes to generate heat to create electricity. Because they’re in deep space they don’t have to worry about the radiation affecting people and animals, just the modules on the space probe itself.
Of course, launching nuclear materials into space is a really bad idea. Space launch technology isn’t exactly foolproof, and every so often things explode, or go the wrong direction. Congratulations, you’ve just spread nuclear waste all over Florida.
There are much much cheaper ways of dealing with nuclear waste. Like, digging a deep hole in an area with no ground water, and piling it in there. That’s what the Yucca Mountain facility was supposed to be. Except Nevada got mad that they had to accept the nuclear waste from all over the country. The other problem is transportation of the waste from all the generating sites all over the country to the repository. Trains are a lot safer than rockets, but we still have massive train wrecks every so often, often causing nasty chemical releases.
And so we have the situation we have now, which is where nuclear sites mostly retain the nuclear waste they generate on site. This has the advantage of reducing transportation, and the nuclear site is already a nuclear site. The problem is that a lot of sites aren’t really suited for long term sequestration of nuclear materials, due to extensive groundwater, potential for earthquakes or floods, and so on.
But the notion that nuclear waste is so dangerous that we have to remove it from the planet to be safe is just silly. Low level waste will be dangerous for thousands of years, but that’s because it is decaying really slowly. The really dangerous isotopes fission really quickly, that’s what makes them dangerous.