Hypothetical scenario: If we change the case fill% by just tinkering with case size WITHOUT changing anything else like seating depth, powder qty etc etc...what should happen to the pressure in chamber? WIth lower fill % will pressure go up or down? what will happen with higher fill %?
Wow, you're jumping into the deep end early.
As pointed out earlier, same amount of powder, lower fill percentage means more case capacity.
The direct answer to your question is the peak pressure will go down for powders and charge weights reasonably applicable to your application. With the larger case, you'll need to add powder to restore peak pressure. The larger case, using more powder to restore the peak pressure to previous levels, will have a higher velocity because the larger starting volume and increased powder mass will maintain a higher average pressure in the barrel.
For the same barrel length, increasing the mean pressure doesn't have nearly as strong effect on the velocity as the peak pressure. Rifle bullets fired from high performance cartridges typically acquire about 1/3 their final velocity by peak pressure. This is the core of the overbore problem. You can partially offset it by using more of a slower powder in the larger case, but you're still working on the average pressure.
QL is not a reloading manual. With the 33XC you're working with, it's a bit like a high performance motorcycle. It'll launch you over a cliff as cheerfully as it'll take you down the road. It will provide a lot more warning than the internet that you're doing something stupid if you pay attention. A lot of the information out there on the 33XC is somewhere between irrational exuberance and really stupid. The core fallacies seem to be maximum velocities give maximum performance and the bullets will operate well at any pressure the case will take. With the Tubb brass and jacketed bullets, it's straight forward to demonstrate that neither is true but you'll have to do your testing at over a mile to see it. The Tubb brass will hold primers after repeated firings at eye watering pressures. When your copy of QL arrives, use 0.35 as the weighting factor, 12,000 psi for the start pressure and fill in the rest of the required data from your ammo. Adjust the start pressure to match the velocities for your ammo. By the time you're to 16-18,000 psi for the start pressure to get the velocity to line up, the barrel is either done or you've entered a feedback loop. The start pressure drives up the peak pressure which drives up the start pressure which drives up the peak pressure, ....... At that point, you're exiting the exuberance phase. The first time you do that, you're going to be very disappointed with the velocities.
The velocities need to be recent because with overbore ELR cartridges they will rise until the barrel dies if you maintain constant jump. With a cartridge as overbore as the 33XC, you'll need to adjust the load every box of 50. My first one was good for 300 rounds before the performance beyond a mile deteriorated noticeably. 100 yard accuracy was done by 450. What kills the extended long range performance isn't the loss of precision, it's the contribution of the barrel to BC variation and it's impossible to discern inside of a mile. That was my first barrel with the cartridge and I viewed it basically as a lab rat. Early on, I shot a lot of high pressure rounds in 10 shot strings using double base powders to generate performance data to select bullets with.
On barrel life, there is no point in trying to preserve it. You can extend it some, but why? A barrel's life should be judged on what you learned from it or how many hits it provided. Test it like you intend to use it. If you're going to shoot a 10 shot course of fire, shoot 10 shot groups and evaluate velocity spreads from a 10 shot perspective. If that seems like it's going to hurt too much, move back to a 300 Norma or 300 PRC to do your rites of passage. That's not intended as a slam.
If you buy, read and internalize the latest Litz book, you'll save yourself a lot of time and components.