Your problem is that much of the terminology of thermodynamics was defined before the underlying physical concepts were properly understood, which leaves us stuck with a lot of confusing names for things now.
In particular, you're worried about the applicability of the quantity commonly known as the "specific heat capacity at constant volume". The first thing you need to know is that that's a misleading name for the quantity, for two reasons. The first reason is that "heat capacity" is an oxymoron: "capacity" signifies storage, but we now know (originally from Joule, 1845, Lond. Edinb. Dublin Philos. Mag. J. Sci. 27(179):205-207) that, when it's being stored, energy doesn't have an identity as "heat" or "work", it's just energy; it only develops an identity as "heat" or "work" when it's being transferred. The second reason is that, as you've noticed, it's important even when the volume is not constant.
Therefore, a better name for the quantity commonly known as the "specific heat capacity at constant volume" would, following Stedman (1963, Educ. Train. 5(3): 127-128), be "specific internal energy capacity". It is, as that name suggests, the quotient of the change in specific internal energy of a body by the change in the temperature of that body.
Now let's think about the situation you're trying to analyse: an isentropic non-flow process, in which some material is compressed. In a non-flow process (unless something exotic is going on), internal energy is the only form in which the material can store energy; and "isentropic" implies that no heat is transferred, so the only way in energy can get in or out is as work. Hence, the specific work done is equal to the change in specific internal energy, which is (by definition) equal to the product of the specific internal energy capacity and the change in temperature, as your first equation says.
Now you may be wondering how the specific internal energy capacity came by the misleading name "specific heat capacity at constant volume" in the first place. Well, think about an isochoric (i.e. constant volume) non-flow process. As before, in a non-flow process (unless something exotic is going on), internal energy is the only form in which the material can store energy; and if the volume is constant in a non-flow process (again, unless something exotic is going on), then no work is done, so the only way energy can get in or out is as heat. Therefore, the specific input of heat is equal to the change in specific internal energy, which is (by definition) equal to the product of the specific internal energy capacity and the change in temperature, i.e. in an isochoric non-flow process, the quotient of the specific input of heat by the change in temperature is equal to the specific internal energy capacity. The quantity that Stedman and I suggest should be called "specific internal energy capacity" was first discussed in the context of measurements of the specific input of heat required to bring about a change in temperature in an isochoric process, before anyone knew about the interchangeability of heat and work or the idea of internal energy, and hence it got the name "specific heat capacity at constant volume" with which we seem to be stuck today.