Despite using an 100pin LQFP, it looks like you are pretty green at this. To break it down simply, you want 100nf caps as close to the power pins as possible. You use one capacitor for each power/gnd combo, meaning if you have 5 power pins and 5 gnd pins, you have 5 caps.
Place the caps inline with the power delivery. I've attached a sample of placement.
If you want to research it more later, you can, but this is all you need to know to get your board done and this is how decoupling is done on 99% of boards that you see with common non-BGA microcontrollers. Don't worry about multiple cap sizes or multiple caps on the same pins at this point.