Everything that has been said so far is accurate with the exeption of needing to add insulation (possibly). When you find frost “spots” in an attic, rather than large frosted areas, it usually means you have warm air leaks into the attic. I noticed you said the house is 45 years old. Very likely, items like vent fans, light openings, recess lights were never cauked to air seal them. Most people never know how much energy is lost as well as how much condensation takes place in the attic where hot air escapes.
Most of the roof leaks our warranty department responds to is only condensation. Once you get over an R-50 in an attic, adding more doesn’t give you much in the way of returns. Plus, the dew point will will be at some level in the insulation. The key to not have condensation at the dew point is to not have air transfer through it.
If you do have a leak or condensation on the underneath side of the roof sheathing, it will appear discolored and obvious.
As for painting the discolored spot, make sure it is completely dry before applying Zinser product!