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Setting both "System" and "Global" sub-option values at once seems to work:

SetOptions[EvaluationNotebook[],   
    "AutoStyleOptions" -> {"SymbolContextStyles" -> 
      {"System" -> RGBColor[211./255, 54./255, 130./255], 
       "Global`" -> RGBColor[181./255, 137./255, 0./255]}}]