What is the file’s Colour Space?
Please set the Status Bar to »Document Profile« and post a more meaningful screenshot.
What are the Edit > Color Settings?
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Numbers are relative to color space. The same numbers yield different actual colors in different color spaces.
You probably think hex numbers are "absolute", lots of people mistakenly assume that, but they mean nothing until they refer to a specific color space (sRGB, Adobe RGB etc). Hex is just a different notation for RGB values.
For screenshots, you can't use the color picker directly. You must first assign the monitor profile, then convert to the same color space the original is in. Then the numbers will match.