In LEO and during a night pass, it is possible to see a lot more than from our places (but just a little more than from Namibia, for instance).
For that, the room the astronaut is occupying must have no light (if someone is working right next to the gazer, no chance of darkness) (so that no light is reflected on the window). The gazer will also need 10 minutes for his eyes to get used to darkness.
The astronauts do see stars, but they need to get prepared for it.

On your way to the Moon or Mars or back to Earth.....much less chance because the Sun is always there. Even if hidden by the spaceship's structure, the slightest illuminated antenna at eye sight will prevent eyes from viewing faint objects.

Now, on the Moon's farside, while the Sun is not there...that would be ideal! But the equipment might not be very interested in extremely cold temperatures