Multiply is a blend mode makes things darker. I guess that would make it kind of like those other features in Photoshop, Darken/Color Burn/etc. (I don't know much about them, sorry) but I like Multiply the best because it seems to "add on" to the layers below it the best, without making super neon or ugly colors, and is good for shading (like, if you make a multiply layer with a blue color, then the shadows on your drawing will be blueish). I'm sorry, I don't really know how to explain it! I mainly discovered how Multiply works through trial and error. My best advice would be to test it out yourself; try shading something with a multiply layer, and experiment with what colors you use until you find one that looks good!
And don't feel bad about asking questions! I'd love to help you out the best I can, so if you're confused with anything else, ask away!