The best way to keep a steam Iron in top working order is to follow the manufacturers instructions, but there are some very good things that my Mum taught me.
If possible use Ionised water, the type that is put in car batteries. This reduces the amount of hardness in the water and stops the Iron from Furring Up.
Always empty the excess water out before storing the iron. Stale water smells bad and will leave a musty smell on your clothes. Allow the iron to cool in an upright position with the steam level on full which allows the small residue that cannot be poured out to exit through the steam vents and leaves the inside of the iron drier.
Dont try to use the steam function before the iron is fully warmed up, or when using a low heat setting as this will leave watermarks on the clothes and will clog the steam vents up as the water hasnt got hot enough to produce steam.
If the iron has a Self-Clean system for unblocking the Steam Vents, then use it. At least once a month, but I tend to do it every time I use the iron.
Dont use the iron for just a couple of Items. Using for just a short time means that the iron has to heat up and then cool down quickly, which in turn means that the elements life is shortened.
All in all, if you follow the instructions which come with your specific Iron, then it should give you many years of good service.