Of course, if you find them in breeding condition in the same place at the same time, and there are consistent and non-overlapping differences between them (no matter how small) then they are almost certainly different species.
The only time there is a problem (if you are using the biological species concept) is if you have somewhat different populations living in different places that are not in contact. In this case, you cannot definitively determine if they would interbreed of they were in contact.
In practice, what is done is to evaluate the degree of difference (especially in characters related to courtship and breeding) relative to other pairs of related species that are known to be non-interbreeding. And the degree of difference that is acceptable to consider them different will differ according to group, as will the characters considered. For example, in Birds-of-Paradise one might look at differences in the elaborate plumes used in courtship display. In flycatchers, in which many species look very similar, you would consider differences in call.
In many insects and other animals, the male genitalia differ in form between species. In this case, you could be sure the forms couldn’t successfully mate even if they were not in contact.
There are so many undescribed species out there, at least in insects and smaller groups of animals, you shouldn’t be surprised at all to hear about new ones. We’re only just scratching the surface after 200 years of cataloging.
Those are both extremely unusual cases. Modern humans are more widespread than almost any other species. However, how an extraterrestrial would catalog human populations would depend on how thoroughly they had sampled them. In the 19th century, distant populations of many widespread populations of animals were classified as separate species. As scientists collected in the regions in between, they realized there were intermediates and they were the same species.
Back in the early to mid 20th century, there was a period of lumping when taxonomists combined many formerly separate species. Now, however, due to genetics, it appears that this lumping went too far, and many species are being re-split because genetic studies indicate that they do not interbreed.
Dogs are really much more variable than virtually any other animal species, but this is maintained by artificial selection and not a good example to evaluate typical species differences on.