The idea rainwater picks up pollution is a bit of a myth. Assuming you don't live next to a Union Carbide factory or something, in the time the rain takes to fall down to the ground and flow off the roof it will pick up much less muck than, say, the water passing through the pipes on its way from the water works to your house. In terms of chemical composition it will be much cleaner than the water you already have in the aquarium since it won't have any nitrate or phosphate, let alone hardness.
If you really are worried, you can filter the rainwater through carbon. Use a small canister filter, fill it with carbon, and stick it in the bucket for half an hour before you use the water. But I don't bother usually, and never had any problems. The reverse in fact: many fish breed much more easily in soft water than hard.
Collecting the rainwater is the trick, though. I simply cut away a piece of the downpipe from the guttering of my house, and directed the outflow into a plastic barrel. You can buy rainwater butts for about 20 pounds, and compared with the hassle and expense of reverse osmosis, it's money well spent. Of course it is also ecologically very sound and saves you money, since you're not wasting municipal water. I suppose it's only viable if you live somewhere with regular rain (which, if nothing else, the UK has!) but other than that, it's something every aquarist should try.
Cheers,
Neale
rain water

wow thats a good idea
id just watch out for pollution if you live in a place where there is
I agree that chaning the pH is tricky if you don't change the hardness as well. But if you reduce the hardness, for example by using rainwater, then the pH largely takes care of itself. Soft water tends to acidify over time, and especially so if you add peat to the filter (a good idea with rams and cardinals). Nonetheless, you should monitor pH, at least at first so you get a "feel" for how your aquarium works with soft water. I have experienced a sudden pH crash in my aquarium following a sudden die-off of plants; such pH changes don't happen in hardwater aquaria because they are self-buffering.
If you do use soft water, it's worth switching all your fish to those preferring soft, acid water. For one thing, they tolerate low pH events well. Cardinals and rams will both tolerate a pH below 6, giving you a day or two to spot problems and fix them. Hard water fish can die within hours at such a low pH. I also add some hard water (i.e., tap water) at a ratio of about one part hard water to 10 or 20 parts soft water. This gives the aquarium a bit of buffering and helps keep the pH at a manageable 6.5.
Cheers,
Neale
6.5 PH will even see them readily breed and spawn. this ph is also ideal for the cardinals. saying that i dont feel its worth thinking about adjusting your PH this is a black art at best really.