I've noticed that a few times, too. There however seems to be no way to get around it as I think it's got something to do with the conversion of 360° H-value to 0-100% 💡
It's almost like the colour picker is HSV but the values it's trying to store are being converted to Hex or RGB. I suspect the colourspace used for the editor might be doing some conversion between RGB colour and HSV.. this is doable mathematically, so inevitably there make be some rounding error.
If you want a dull read
http://www.niwa.nu/2013/05/math-behind-colorspace-conversions-rgb-hsl/
Matching colours can be a pain and I suspect the same as MatskiMonk that it's a HSV/B-RGB conversion or rounding issue.
My work around for the colour jumping (and workflow for creating a working palette for new liveries) is as follows:
Step 1. Set the values you want - e.g. 45 55 65 hit ok.
Step 2. Go back into the colour picker, You'll notice that the cursor jumps to the picker and that the newly created chip is not highlighted (this is because the picker is correct but the chip has the wrong values) - Select the new chip
then go to the picker, as you'd expect, one or more of the values will be 1 digit out - e.g. 44 55 66 - adjust the figures back to where you want but go one higher/lower - e.g. 46 55 64 hit ok.
Step 3. Repeat Step 2. until you have a chip that's values are correct (this takes a bit of trial and error but you will get there in the end).
Step 4.
(This is a good tip if you need to preserve a colour between sessions or want to clear up the recent colours palette to avoid selecting the wrong colour) Paint any part of the car with the correct chip (If working with multiple colours paint multiple areas with the required colour) and Save the livery (I sometimes do a save as and create a 'Palette Car' with colours I need to preserve.
Step 5. Exit the Livery Editor back to the main screen.
Step 6. Open the livery (either the 'Actual' or the 'Palette' version, whichever you painted the car in) then go into the paint selection.
Step 7. Select the area painted in the required colour and open the colours, the cursor should jump to the picker (if it jumps to white then you will need to repeat the above steps again). Open it and hit ok and exit the colours.
Step 8. Re-open the colours and the colour chip should now be selected (You can verify the values to make sure it's correct).
As the livery editor no longer allows you retrieve a custom colour used for a decal this method also helps you retrieve colours between sessions if you need to leave the editor at all. Simply paint any part of the car in the needed colour prior to saving.
In regards to custom colours, so long as you don't exit the Livery Editor the working colour palette is saved between liveries, hence why you can paint a random car in colours you need and use it to retrieve them before opening the livery you're currently working on.