Hubble's Law only applies to nearby space! We assume the whole Universe is expanding at the same rate as our local part of space right now, of course, but the expansion rate
changes over time, and because light takes a finite time to travel we see distant galaxies as they were millions or even billions of years ago. That means, if we measure the distance to a galaxy 10 billion light years away and measure its recession velocity we see it as it was 10 billion years ago* and therefore get a measure of the Universe's expansion rate and Hubble's constant as it was
10 billion years ago, not today!
Astronomers are therefore not content to simply use Hubble's Law to naively predict the distance to distant galaxies based on their recession speed, and are constantly seeking to measure the distance to far away galaxies using methods
independent of Hubble's Law, and to measure their recession velocities. That way we can both measure the distance to distant galaxies and study how the Universe's expansion rate has changed over time.
So your question really boils down to "How can we measure the distances to distant galaxies without needing to use Hubble's Law and break the chicken-and-egg loop?" Ironically, the answer to your question is in your PF username! ^_~ Type Ia supernovae are known as
standard candles - objects of known luminosity (all type Ia supernovae explode at the same luminosity, because the explosion is always the same. A type Ia supernova happens in a binary system where two stars of different masses evolve at different rates. One star dies and becomes a white dwarf; the other evolves more slowly and expands to become a red giant. Since the two stars are in close contact, and the red giant star is pretty large and distended, material from this star gets gravitationally attracted to the white dwarf and spirals down onto it. This transfer of mass continues until the white dwarf reaches the Chandrasekhar limit - the upper limit for the mass of a white dwarf, about 1.4 solar masses - collapses and explodes. Because this happens at the same mass for all type Ia supernovae, the physics of the explosion would be identical for all type Ia supernovae and hence they all have the same luminosity). Since we know the luminosity of the supernova, and can measure how bright it appears from Earth, it's a simple calculation to work out how far away that supernova must be. (There are other standard candles too, like Cepheid variable stars, but type Ia supernova are very bright and hence useful for very distant galaxies.) For more about standard candles and using them to get distances to astronomical objects, read this:
http://www.astro.ex.ac.uk/people/hatchell/rinr/candles.pdf
Of course, type Ia supernovae are quite rare - they happen once every century or so for any individual galaxy. But there are a LOT of galaxies out there, and if a telescope is focused on a particular patch of sky for long enough, a few type Ia supernovae are bound to happen in it. Doing this for many different patches of sky and finding the distances to many galaxies using this method and measuring their recession rates has helped cosmologists work out how the Universe's expansion rate has changed over time and therefore calculate the age of the Universe. See the
Supernova Cosmology Project for an example - they're the group who used supernovae in 1998 to measure the distance to many galaxies and discovered that for the last few billion years the Universe's expansion has been accelerating!