I'm ashamed to admit it, but I don't think I've ever been able to genuinely motivate the definition of a topological space in an undergraduate course. Clearly, the definition distills the essence of many examples, but it's never been obvious to me how it came about, compared, for example, to the rather intuitive definition of a metric space. In some ways, the sparseness of the definition is startling as it tries to capture, apparently successfully, the barest notion of 'space' imaginable.
I can try to make this question more precise if necessary, but I'd prefer to leave it slightly vague, and hope that someone who has discussed this successfully in a first course, perhaps using a better understanding of history, might be able to help me out.
Added 24 March:
I'm grateful to everyone for their thoughtful answers so far. I'll have to think over them a bit before I can get a sense of the 'right' answer for myself. In the meanwhile, I thought I'd emphasize again the obvious fact that the standard concise definition has been tremendously successful. For example, when you classify two-manifolds with it, you get equivalence classes that agree exactly with intuition. Then in as divergent a direction as the study of equations over finite fields, there is the etale topology*, which explains very clearly surprising and intricate patterns in the behaviour of solution sets.
*If someone objects that the etale topology goes beyond the usual definition, I would argue that the logical essence is the same. It is notable that the standard definition admits such a generalization so naturally, whereas some of the others do not. (At least not in any obvious way.)
For those who haven't encountered one before, a Grothendieck topology just replaces subsets of a set $X$ by maps $$Y\rightarrow X.$$ The collection of maps that defines the topology on $X$ is required to satisfy some obvious axioms generalizing the usual ones.
Added 25 March:
I hope people aren't too annoyed if I admit I don't quite see a satisfactory answer yet. But thank you for all your efforts. Even though Sigfpe's answer is undoubtedly interesting, invoking the notion of measurment, even a fuzzy one, just doesn't seem to be the best approach. As Qiaochu has pointed out, a topological space is genuinely supposed to be more general than a metric space. If we leave aside the pedagogical issue for a moment and speak as working mathematicians, a general concept is most naturally justified in terms of its consequences. As pointed out earlier, topologies that have no trace of a metric interpretation have been consequential indeed.
When topologies were naturally generalized by Grothendieck, a good deal of emphasis was put on the notion of an open covering, and not just the open sets themselves. I wonder if this was true for Hausdorff as well. (Thanks for the historical information, Donu!) We can see the reason as we visualize a two-manifold. Any sufficiently fine open covering captures a combinatorial skeleton of the space by way of the intersections. Note that this is not true for a closed covering. In fact, I'm not sure what a sensible condition might be on a closed covering of a reasonable space that would allow us to compute homology with it. (Other than just saying they have to be the simplices of a triangulation. Which also reminds me to point out that homology can be computed for ordinary objects without any notion of topology.)
To summarize, a topology relates to analysis with its emphasis on functions and their continuity, and to metric geometry, with its measurements and distances. However, it also interpolates between these and something like combinatorial geometry, where continuous functions and measurements play very minor roles indeed.
For myself, I'm still confused.
Another afterthought: I see what I was trying to say above is that open sets in topology provide an abstract framework for describing local properties of functions. However, an open cover is also able to encode global properties of spaces. It seems the finite intersection property is important for this, but I'm not able to say for sure. And then, when I try to return to the pedagogical question with all this, I'm totally at a loss. There are very few basic concepts that trouble me as much in the classroom.