No, ShadowPlay is not a full-on streaming program (suite), so you won't be able to create different scenes to switch between. The only programs which allow for "scenes" like that are streaming programs, such as OBS or XSplit. However, neither OBS or XSplit use their own codec like an actual recording program does, and they just tap into what already exists on the internet. Programs like FRAPS, BandiCam, Action, or DxTory all use their own proprietary versions of H.264 (or similar) to capture video footage, but some of them, like BandiCam and DxTory, can also use other "external" codecs (e.g. x264, Lagarith, MagicYUV, etc) to record with.
I think ShadowPlay is worth a shot, but it's certainly not a streaming suite (although I think nVidia is trying to get it there), and it sounds like you want more of a streaming program/suite so that you can record different monitors at different times.
As far as I know, NVENC (short for "Nvidia Video ENCoder") is the GPU-accelerated H.264 encoding that ShadowPlay uses. If there is somewhere that you can point me to which says ShadowPlay doesn't use NVENC, then I'll read it. However, I have no doubt that nVidia is doing something slightly different under the hood of their own program because I've tried to reproduce the results with OBS and NVENC, but was unable to (this was months ago). Maybe I'll try again in the future after my new machine is completely finished, because that was when I was still on Windows 7, and perhaps Windows 10 changes the playing field.
ShadowPlay certainly doesn't truncate my videos based on filesize, so I'm not sure why you're experiencing that unless, perhaps... You're using a 32-bit operating system?
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