I gotta weigh in on this one. I believe steam is inherently less reliable than modern diesels for a number of reasons. First of all there are a lot more human factors that enter into steam construction, maintenance, repair, and operation. This is probably the biggest single factor because it affords many opportunities for something to go wrong whether it is the wrong water treatment, bad firing practice,lack of lubrication, etc., etc, etc. Typically steam locomotives will operate with many more things out of design tolerance than more modern machines. Unfortunately this opens the door to letting things go because they still work. It runs - but for how long.
I agree with Earl that the key is vigilance at all times. This is the only way to minimize breakdowns. It starts at the beginning with what material is being used in manufacture or repair. It then goes to material handling, working, and finish. A quarter inch undersize piston will work but it becomes a failure point sooner rather than later. Chrome-moly staybolts will work but probably not for long.
I believe it is possible to improve the reliability of steam locomotives using more modern techniques and sometimes materials. The two items most affecting the reliability of these beasts are competence and money. If you short yourself on either one there will be problems. You only have to look at the many projects over the years done by "experts" on the cheap for verification. Even with the best care, most qualified people, and loads of money, there are still a million booby traps on every steam engine.