Addition is for accumulating measurements. Multiplication is for forming a new type of composite measurement.
Addition accumulates measurements
If I have a ruler, I can walk it along the boundary of my room, and if I'm careful to keep it level and make successive measurements end to end, I'll have a guarantee that the sum of the individual measurements is a physically meaningful quantity, namely the total perimeter of my room. You can do the same for time, or temperature, or pressure.
Adding mixed units such as meters and seconds is not invalid; it's just that addition is supposed to be for accumulating successive measurements, and we don't have a real world process (like walking the ruler) that corresponds to accumulating measurements of different types. Certainly if you add the numerical values of measurements with different units, you'll get nonsense.
If you like, you can say you are allowed to make sums out of mixed units, it's just that (a) they don't simplify (they have to stay as "5km + 3sec") (b) they don't systematically correspond to any real combined quantity.
Multiplication creates composite units
In contrast to addition, which accumulates measurements, multiplication creates new sorts of measurements.
For example, if you measure the rate of energy consumption of an appliance to be around 5kW, and you run it for three hours, the total energy consumption is 15 kW*hr. This is not a sum of several little measurements and it's not new information; it's a way of combining two related quantities you've measured to get at the value of a third quantity (like energy) without needing a special instrument.