Unfortunately as with many controls both Toolkit and otherwise there often many different places where color is used other than simply Foreground and Background. These colors are "hardcoded" into the Templates of the controls. This requires that you supply a new template to the control in order to modify these colors.
You need fo clone the existing AccordianButton
template, either using Blend if you have it or you'll find in the source code here
Silverlight3\Source\Controls.Layout.Toolkit\Accordion\AccordionButton.xaml
So you basically have in your application a resource dictionary containing this style:-
<Style x:Key="MyAccordionButtonStyle" TargetType="layoutPrimitivesToolkit:AccordionButton">
<Setter Property="Template">
<Setter.Value>
<ControlTemplate TargetType="layoutPrimitivesToolkit:AccordionButton">
<!-- Adjusted Clone of template here -->
</ControlTemplate>
</Setter.Value>
</Setter>
</Style>
The parts of the template you would want to tweak are the two Border
element named "ExpandedBackground" and "MouseOverBackground". These have hardcoded Background values that you will want to modify. You may also want to look at the Stroke
property on the "FocusVisualElement" Rectangle.