The $r$ value in this equation represents the separation of the two bodies' centers of mass.
So, when you're standing on the surface of the earth, then the value of $r$ is equal to $r_E$, the radius of the earth, which is $6378$km or $6.378\times10^{6}$m.
To answer your more general question, the force between two masses does, indeed, increase as separation decreases, but as separation gets smaller and smaller, other forces start to dominate.
The electrostatic forces between molecules and atoms are millions of times stronger than the gravitational forces between them.
The strong nuclear forces between nucleons are even stronger still.
Still, if you have enough mass, gravity can overcome all of these forces. When a large enough star collapses to an ever-smaller point, you get a black hole. While Physics tends to try to avoid talking about infinities, the nature of a black hole is such that you can, in theory, get arbitrarily close to its center of mass.
However, at this point, you are lost to the universe and what happens inside a black hole, stays inside a black hole. Physicists are not really sure what happens there.