In layman's term, there is a certain sweet spot where a psu peaks in its efficiency, and that is around 40 ~ 60%. Do note though, it is quite a small, negligible % amount so it does not translate to much more savings overtime because of the initial price you have to pay for a higher wattage psu.
However, it is advisable to try and fit into that range not only for efficiency reasons, but for deteriorating components like capacitors due to prolonged usage and heat which decreases the max output of a psu overtime.
By your example, if I have a pc requiring 400W max, I would probably go for a psu that is around 600~650W.