No, doesn’t work that way. You need a knob that let’s you set the balance between the cue and the master signal in your headphones.
You can of course hit both cue buttons and get both sounds in your ears, but they will be the same relative level.
A trick could be to turn up the gain on the cue channel, just don’t go into the red and remember to turn it down to the right level before the actual transition (at which point you can’t use this trick of course).
In general I would say what you want won’t work on this controller.
It works on most other starter controllers we shortlist, like the Numark MixTrack Platinum (Pro has it also I think), the Reloop Beatmix 2 mk2 and even the now a bit dated MC2000 has cue/master panning. All of those won’t work (easily) with RekordBox DJ, so in that case you are stuck with Pioneer gear.