It can be difficult; fish vary so much that any 'diagnostic' feature may not be present in all species in that family.
For example, most tetras have an adipose fin (a small, 'false' fin, just in front of the tail), but it's absent in the silvertip.
Even 'tetras' themselves are no longer considered a good genus, as they've been found to be not as closely related to each other as previously thought.
There's really no reliable way of identifying fish just by looking, although you can make some informed guesses. Most people can easily learn to recognise Rift Valley cichlids, but identifying the actual species can be very difficult and sometimes involves techniques that we can't do as hobbyist, really, like counting pharyngeal teeth.
The only real, reliable way, is to find out the actual, scientific name of the fish and look it up!