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It's not easy for us learners. (For native speakers, it's natural). Here's a start:
In Spanish, there is a difference when using estar (of which está is third-person singular present indicative form) and ser (which would be "es" in this specific case). Although they both mean "to be", the particulars are not as simple but you could say that ser is used when referring to permanent conditions and estar when referring to a temporary, actual conditions. When you say "Mi tía está sola" it means she is alone right now but probably wasn't always or won't be in a few moments.