You can also go to the Keybindings page on the options screen. Look for Buy Metal and Buy Crystal. They're bound to something initially, but I changed them to F5 (metal) and F6 (crystal).
It's a lot easier to just punch the button a few times than have to muck about with the black market UI. Plus you don't lose track of what's going on in the game.
Edit:
Travel to a new solar system by researching the appropriate drive technology in the military tree. I don't know the names offhand, but it will say something to the effect of "Allows travel to distant star systems". After you've researched it, move your fleet to a star, then right click the star you want to go to.