The CPU reading from Asus Probe may or may not be accurate. That reading is typically an approximation of what the TCase reading is but I don't have enough experience with your board to know how accurate that is. On my older Asus P5B board, this reading seems to be close at idle but it reports at least 25C too high at full load so I don't trust it too much.
Your results are hard to interpret. Usually when you switch coolers, the temperatures decrease but they decrease similar amounts on each core. Your first screen shot looks a lot different from the one above for core to core consistency. Maybe you're getting better at installing a heatsink.
How much heat paste do you use and what method do you use to apply it?
At the moment, TJMax looks 5C higher on core 2 but the other 3 look like they are all the same. I've seen CPUs where two cores have one TJMax and the other two cores have a different TJMax but never 3 with one TJMax and 1 with another.
If you set TJMax to 100, 100, 105, 100, you should have consistent temperatures across all 4 cores from idle to full load. Intel doesn't provide enough documentation about these sensors so that is just my best guess.
Your core temps do seem higher than normal. Some of these sensors read higher than normal by 5C or 10C at idle so that's not unusual. The test I use to try to figure this out is I open my case, turn the CPU fan to high if it's adjustable and then I go into the bios and boot up at 333 x 6.0 and manually set the core voltage as low as it can go. My board will boot up at 1.08 volts. This creates a minimum amount of heat. After that I let my computer sit there after booting up at idle and see how low the temps go.
If you don't want to change those bios settings then just enable EIST / SpeedStep and C1E. When you get to Windows, run CPU-Z and see how low your core voltage goes and if your multiplier goes down to 6.0 like it should.
With 45nm Quads, this test might not give us any new information because of the problem with sensors getting stuck at lower temperatures. If you're curious, try that and post your results and we can go from there.
You might be better off using TJMax = 95, 95, 100, 95
It might not be accurate at full load but might be more accurate at the temperatures you typically operate at.
As for overclocking, the 7.0 maximum multiplier is going to limit you. I would try to run it at 7 x 500 MHz but very few motherboards can run a Quad stable with a FSB of 500 MHz. Start by trying 400 MHz first and go from there. You have enough core voltage that you can probably get up to 450 MHz without having to adjust that. You might have to adjust northbridge voltage and a few other voltages as well. It would be best to find a forum with users that specialize in overclocking 45nm Quads on your motherboard for some pointers.
With your new cooler and a 7.0 multiplier, temperatures will be fine so worry less about how accurate they are, because they're not, and concentrate on doing some overclocking.