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See diagram for clarity.  The  speed of the train with respect to the car or, as seen from car is given by
           V_train - V_car  = vector subtraction.
 SO draw - V_car  in West and then add.  It is the diagonal of the rectangle.

         magnitude of the relative velocity = √(60² + 80²) = 100 kmph
 Direction =  Ф towards West from North. 
                 tan Ф = 60/80 = 3/4 ,    Ф = 36.87 deg North West..
       or  53.13 deg from west towards north.