The (promised) benefit is of course a better sound. However note that there are quite a few formats around:
dts 24/96 - requires a matching dts 254/96 decoder; only found on newer AV amps/receivers (but is IMHO backwards compatible though it will play then at 48kHz only)
DVD-Video 24/96 - IMHO the first attempt at a high resolution audio format before DVD-A and SACD were available, also allows short video clips or still pictures; requires a 24/96 decoder inside the player or the AV amp/receiver
DVD-Audio 24/96 - one of the possible formats of DVD-A (max. 24/192). Requires a DVD-A compatible player and usually the decoding is done in the player as there is currently no digital interface for transferring DVD-A (beside some proprietery solutions)
Well, 24-bit 96kHz DVDs (DADs) exist, while 24-bit 96kHz CDs do not; CDs are restricted to 16-bit 44.1kHz.
Your Pioneer includes 24-bit 192kHz DACs so DAD discs will be heard at full resolution from the player's analogue RCA outputs. The player is also capable of outputting 24-bit 96kHz material from its digital outputs, allowing external processing by suitably equipped amplifiers and processors.
While you are capable of playing DADs, they are quite uncommon.
There isn't much in the way of non-MLP packed 24/96 material to listen to nowadays. Some DVD-Audio discs include a standard 24/96 soundtrack and DADs can be purchased from companies such as Chesky.
I'm not familiar with the A5, but if it includes 24-bit 96kHz DACs then DADs should work fine with it using the Pioneer player. You can also use the DVD player's DAC if you so choose, via its analogue outputs.