It's better to use when introducing fish to the tank. It does nothing as far as filtration is concerned as it's basically a supplement for the slime layer of the fish, which is like their outer most barrier against sickness.
Add it about 10min before adding fish to the tank. You can also add some whenever introducing additional fish to the tank.
If you plan on doing a complete water change and/or redecorating the tank you could add Stress Zyme.
It isn't a necessary supplement if you have an established tank and do regular water changes, as these won't stress the fish out too much.
Just out of curiosity but when I bought my new rnk it came with two bottled of stress zyme but I noticd that they are around 2 years out of date. Are they still ok to use? I don't know what is actually in them to deteriorate hence why I'm asking.
Cheers.