No way to calculate exact amount, as it depends on things dissolved in water. Rain water is typically rather soft and clean, so it shouldn't be a serious factor, but one never knows. In the end it is not about using calculated amount of water, but about adding acid till you get to the desired pH.
Assuming pure water and no interference to get pH of 4.5 you need sulfuric acid concentration in range of 10
-5 M. Adding a single drop of the concentrated acid will probably overshoot by orders of magnitude. I would start by diluting the concentrated acid 100 times, then the volume needed to acidify the rainwater would be more manageable, in mL range. It can be still too much for precise adjustment, but then getting exact pH with just an acid (and not a buffer) is always tricky.
That is, unless I didn't make any mistakes in my math at 9 a.m.