Its difficult to give a single clear answer, because there are many exceptions to this rule. But, essentially, "estar" is used to express something temporary, or a state of being which exists at one particular moment in time, whether temporary or permanent. "Ser" is used to express permanent state of being, and to equate two distinct things or concepts (this = that). This is probably as clear as mud, so feel free to send me a message, and maybe we can discuss this more off-line.