Empty space acts as a black body at 3K, so if you cool a spaceship at 300K, empty space is perfectly cold and takes all heat your craft emits.
But if you're near Earth (or Moon, Mars...) the craft receives heat from these bodies. Very important for low-orbiting satellites, and the craft's IR emissivity absorbs heat from these bodies as well as it emits because it's the same wavelength, so emissivity isn't a means of action for this part of the balance.
Both absorptivity and emissivity can be varied a lot. Varying them in opposite directions is more difficult but possible. α can be between 0.02 and 0.99 at least, with 0.2 to 0.9 being rather easy; it depends much on cleanliness. ε can be between 0.01 and 0.99 at least, with 0.05 to 0.95 being rather easy. Corrugations increase both.
Very hot is more difficult and very cold is more. Clean metals can radiate very little, like 0.01 for gold, while absorbing 0.3 for instance. Glass or thin plastic films can be transparent to light but emit IR; they're backed by a mirror to reject light from the object they cover ("second surface mirrors" or SSM). Thin polyimide films commonly absorb 0.3 to 0.6 depending on the thickness and emit 0.9: they're the gold-colour outer skin of satellites. Other plastics would have absorbed less but degrade at Sunlight. Mirrored glass absorbs <0.05 and radiates >0.8; it's special glass that withstands rays, for instance cerium-doped silica, and costs a lot. Do NOT use paints, theses sh*t don't adhere.
Beyond materials, designers put the parts of controlled temperature in contact with a part that has the proper temperature.
This choice results first from the too small heat conductivity of solids. As soon as a craft is 1m wide (and even before), its Sun side is too hot and its shade side too cold, so designers use heat pipes or even active circulation to keep the temperature under control. This permits an active regulation as well.
Then you can have for instance an always-too-cold radiator and circulate to it the amount of fluid that keeps your ship not too hot.
Or you can have a sun shader to keep a telescope very cold, reducing the noise of its cameras.
In many cases a single shader or insulating layer wouldn't suffice, even with very small emissivity, so Multi-Layer Insulation (MLI) was invented, see Wiki for instance.