At A Level, which equation to use is very simple.
λ=hc/E (or E=hc/λ, or E=hf, they are all differenct versions of the same equation) is for photons.
λ=h/mv is for matter (i.e. anything with mass).
Strictly speaking, you need to adapt λ=h/mv when v is close to c, because of relativity (and some here have described how). This will not be expected of you at A Level.