Space stations and Space Shuttles are purpose built
Yes, there are size concerns that others have pointed out, but the bigger concern at the end of the day is that re-entry vehicles are designed from the ground up to take off and land whereas space stations are designed from the ground up for long term exposure to space; so, design choices are made for both vehicles based on what is optimal for each purpose.
A lot of what makes up a reusable reentry vehicle are the features that allow it to re-enter the atmosphere without burning up. When you look at a space shuttle for example, you have Wings, landing gears, heat shields, parachutes, crash seats, etc. which collectively make up about 25% of the vehicle's total mass. None of these features add any value to a space station.
However, because space stations do not have to accomodate all the hatches and surface geometries of theses things, they have fewer points of failure, more efficient use of space, and they can instead use those surfaces for things more relevant to space station design like whipple shields and radiation shielding which improve the station's long term survivability in the hostile environment of space. Space stations also have no "preferred up" meaning that every surface is essentially useful wall space. You don't have areas reserved for walking or that are ignored because they are on the ceiling whereas a space shuttle's interior has to be considered in terms of how ground crews will service it between missions as well as how it will function in space.
Can a space shuttle spend a few days in space within a reasonable margin of safety? Sure, but trying to design a shuttle that could survive in spaces as long as ISS would not be as good at being a space shuttle as a space shuttle, and it would not be as good at being a space station as a space station because of all the compromises that would have to happen to accomodate all of your roles.