Reliability is one of three aspects of somethings' effectiveness.. The other two are Maintainability and Availability...
An interesting paper... http://www.barringer1.com/pdf/ARMandC.pdf discusses this in more detail, but generally,
Reliability is based on the probability that a system will break.. i.e., the more likely it is to break, the less reliable it is... In other systems (other than software) it is often measured in Mean Time Between Failure (MTBF) This is a common metric for things like a hard disk... (10000 hrs MTBF) In software, I guess you could measure it in Mean Time between critical system failures, or between application crashes, or between unrecoverable errors, or between errors of any kind that impede or adversely affect normal system productivity...
Maintainability is a measure of how long/how expensive (how many man-hours and/or other resources) it takes to fix it when it does break. In software, you could add to this concept how long/how expensive it is to enhance or extend the software (if that is an ongoing requirement)
Availability is a combination of the first two, and indicates to a planner, if I had a 100 of these things running for ten years, after figuring the failures and how long each failed unit was unavailable while it was being fixed, repaired, whatever, How many of the 100, on average, would be up and running at any one time? 20% , or 98% ?