There are several people here much more qualified to speak about that, so I shall just give you some pointers now. One of the questions Grothendieck tried to answer when writing "Pursuing Stacks" was — I don't know how he put it, though — "what are the properties of the simplicial category which make it so useful in homotopy theory?" That is where the theory of *test categories* stems from. As Georges Maltsiniotis puts it: "Le slogan de Grothendieck est que toute catégorie test est aussi “bonne” que celle des ensembles simpliciaux pour 
“faire de l’homotopie”." Which means "Grothendieck's motto is that any test category is as "good" as the category of simplicial sets to make homotopy theory." The theory was further developed by Denis-Charles Cisinski. The two books to read on this subject are:

Maltsiniotis's "La Théorie de l'homotopie de Grothendieck", the introduction of which is remarkably well-written:  
http://www.math.jussieu.fr/~maltsin/ps/prstnew.pdf

and

Cisinski's (augmented version of his) thesis "Les Préfaisceaux comme modèles des types d'homotopie":
http://www.math.univ-toulouse.fr/~dcisinsk/ast.pdf

Both are available in SMF's collection Astérisque.

I shall give you more details if nobody else shows up to explain the yoga (I myself have but a smattering of it).

EDIT: Well, here are some details. You are asking: "What is so wonderful about Δ that allows a model structure (and one, moreover, Quillen equivalent to topological spaces) appear?" A somewhat highfalutin answer would be: "$\Delta$ is a test category". Let's try to see what it means. (I am feeling a bit guilty, for what follows is essentially a rephrasing, with the same notations, of some parts of Maltsiniotis's crystal-clear introduction to his book. I hope it will at least benefit those who cannot read French. Please note that Maltsiniotis's book is based on material written by Grothendieck in "Pursuing Stacks" almost thirty years ago.)

The starting point of the theory of test categorie is similar to your question. Namely, Grothendieck seeks to find *all* the couples $(M, \mathcal{W})$ where $M$ is a category and $W \subseteq Ar(M)$ such that the localized category $W^{-1}M$ be equivalent to the homotopy category $Hot$, and such that $W$ is natural in some sense (with respect to the structure of the underlying category). Given the difficulty to answer such general a question, Grothendieck then requires of $M$ to be a presheaf category on a small category $A$. Adding another slight condition on the small category $A$ (requiring that the "nerve functor" $Cat \to \widehat{A}$ send weak equivalences to weak equivalences, where weak equivalences of $Cat$ are those functors the classical nerve of which are simplicial weak equivalences, and weak equivalences in the presheaf category $\widehat{A}$ are those morphisms sent to weak equivalences of $Cat$ by the functor $A/?$), he is lead to define the notion of *weak test category*. One of the properties of such a category $A$ is that the localization of its presheaf category by weak equivalences is equivalent to the homotopy category $Hot$. Of course, the simplicial category is a test category. But it is even better that that. It is a *strict test category*, which implies (by definition) for instance that cartesian product reflects the product of homotopy types. This theory shows, by the way, that the cubical category differs from the simplicial category in this respect: indeed, the category of cubes is *not* a strict test category (but it is a test category, which lies between the two). You might think that, since the categories of cubes is not a strict test category, strict test categories ought to be pretty scarce. In fact, every full subcategory of $Cat$ the objects of which are non-empty, and which is stable under finite products, and one object of which has at least two objects (possibly isomorphic) is a strict test category. 

Actually, there is more than that in the theory. You can ask what are the formal properties of weak equivalences of $Cat$ that make the theory works so well. That is what Grothendieck answered by defining *basic localizers*. Indeed, what you need is just a class $W$ of functors between small categories such that: $W$ is weakly saturated (which means it contains identities, it satisfies a two out of three axiom, and if $i$ has a retraction such that $ir$ is in $W$, then $i$ (and thus $r$) is in $W$) ; if $A$ is a small category which has a final object, then $A \to e$ is in $W$ ($e$ stands for the point category) ; and $W$ satisfies the relative version of Quillen's Theorem A. That's all you need to develop the theory of test categories. Grothendieck then proceeds to rewrite all the theory with respect to an arbitrary basic localizer replacing $W_{\infty}$, the classical weak equivalences of $Cat$.Therefore, for *every* basic localizer $W$, there is notions of $W$-weak test category, local test category, test category, strict test category and so on. Instances of basic localizers are provided by truncated homotopy types.

And here is a theorem: for every basic localizer $W$, for every $W$-test category $A$, there is a closed model category structure on the category of presheaves on $A$, the weak equivalences of which are those defined above and the cofibrations of which are the monomorphisms. In fact, you have to make a slight set theoretic assumption for the this result to hold. It was conjectured by Grothendieck and proved by Cisinski.

OK, now it might still be unclear as to what are the advantages of this theory. One of them is that you can work with other basic localizers than the classical one, related to Artin-Mazur equivalences, which can be replaced by other topos morphisms. (See the first paragraph of page 12 of Maltsiniotis's book for instance.) 

There are much more stuff in Grothendieck's homotopy theory, but I shall limit myself to that now.