I'm not sure if this will still be helpful, but here is my understanding of the Quillen model. Everything correct that I write below, I learned from John Francis. (Probably in the same lecture that Theo mentioned in his comment above.) Any mistakes are not his fault---more likely an error in my understanding.

**Before we begin: Quillen v Sullivan.**

As others have mentioned, Quillen gets you a DG Lie algebra, where as the Sullivan model will get you a commutative DG algebra. As you write, the passage from one to the other is (almost) Koszul duality. Really, a Lie algebra will get you a co-commutative coalgebra by Koszul duality, and a commutative algebra will get you a coLie algebra. You can bridge the world of coalgebras and algebras when you have some finiteness conditions--for instance, if the rational homotopy groups are finite-dimensional in each degree. Then you can simply take linear duals to get from coalgebras to algebras.

**A way to find Lie algebras.**

So where do (DG) Lie algebras come from? There is a natural place that one finds Lie algebras, before knowing about the Quillen model: Lie algebras arise as the tangent space (at the identity) of a Lie group $G$.

Now, if you're an algebraist, you might claim another origin of Lie algebras: If you have any kind of Hopf algebra, you can look at the primitives of the Hopf algebra. These always form a Lie algebra.

(Recall that a Hopf algebra has a coproduct $\Delta: H \to H \otimes H$, and a primitive of $H$ is defined to be an element $x$ such that $\Delta(x) = 1 \otimes x + x \otimes 1.$)

One link between the algebraist's fountain of Lie algebras, and the geometer's, is that many Hopf algebras arise as functions on finite groups. If you are well-versed in algebra, one natural place to find Lie algebras, then, would be to take a finite group, take functions on that group, then take primitives.

A cooler link arises when a geometer looks at *distributions* near the identity of $G$ (which are dual to 'functions on $G$') rather than functions themselves. This isn't so obviously the right thing to look at in the finite groups example, but if you believe that functions on a Lie group $G$ are like de Rham forms on $G$, then you'd believe that something like 'the duals to functions on $G$' (which are closer to vector fields) would somehow safeguard the Lie algebra structure. The point being, you should expect to find Lie structures to arise from things that look like 'duals to functions on a group'. So one should take 'distributions' to be the Hopf algebra in question, and look at its primitives to find the Lie algebra of 'vector fields.'

**A (fantastical) summary of the Quillen model.**

Let us assume for a moment that your space $X$ happens to equal $BG$ for some Lie group, and you want to make a Lie algebra out of it. Then, by the above, what you could do is take $\Omega X = \Omega B G = G$, then look at the primitives of the Hopf algebra known as `distributions on $\Omega X$'.

Now, instead of considering just Lie groups, let's believe in a fantasy world (later made reality) in which all the heuristics I outlined for a Lie group $G$ will also work for a based loop space $\Omega Y$. A loop space is `like a group' because it has a space of multiplications, all invertible (up to homotopy). Moreover, any space $X$ is the $B$ (classifying space) of a loop space--namely, $X \cong B \Omega X$. So this will give us a way to associate a Lie algebra to any space, if you believe in the fantasy.

Blindly following the analogy, `functions on $\Omega X$' is like cochains on $\Omega X$, and the dual to this (i.e., distributions) is now *chains* on $\Omega X$. That is, $C_\bullet \Omega X$ should have the structure of what looks like a Hopf algebra. And its primitives should be the Lie algebra you're looking for.

**What Quillen Does.**

So if that's the story, what else is there? Of course, there is the fantasy, which I have to explain. Loop spaces are most definitely not Lie groups. Their products have $A_\infty$ structure, and correspondigly, we should be talking about things like *homotopy* Hopf algebras, not Hopf algebras on the nose. What Quillen does is not to take care of all the coherence issues, but to change the models of the objects he's working with.

For instance, one can get an actual simplicial *group* out of a space $X$ by Kan's construction $G$. This is a model for the loop space $\Omega X$, and this is what Quillen looks at instead of looking only at $\Omega X$, which is too flimsy. From this, taking group algebras over $\mathbb{Q}$ and completing (these are the simplicial chains, i.e., distributions), he obtains completed simplicial Hopf algebras. Again, instead of trying to make my fantasy precise in a world where one has to deal with higher algebraic structures (homotopy up to homotopy, et cetera) he uses this nice simplicial model. To complete the story, he takes level-wise primitives, obtaining DG Lie algebras.

**Edit:** This is from Tom's comment below. To recover a $k$-connected group or a $k$-connected Lie algebra from the associated $k$-connected complete Hopf algebra, you need $k \geq 0$. And $k$-connected groups correspond to $k+1$-connected spaces. This is why you need simply connected spaces in the equivalence.

I'm not sure I gave any 'high concept' as to 'why Quillen's construction works', but this is at least a road map I can remember.