I believe you will need to define a custom control template for the TabItem, maybe even one for the TabControl. Here is an example of a TabItem that uses a spacer for some separation.
<Style
x:Key="SpacedTab"
TargetType="{x:Type TabItem}">
<Setter
Property="Template">
<Setter.Value>
<ControlTemplate
TargetType="{x:Type TabItem}">
<Border
x:Name="Spacer"
Width="Auto"
Height="Auto"
Padding="0 0 5 0"
Margin="0 0 0 0"
BorderBrush="Transparent"
BorderThickness="0">
<Border
x:Name="Border"
MinWidth="150"
Width="Auto"
Height="30"
Background="Gray"
BorderBrush="DarkGray"
BorderThickness="0,0,0,0"
CornerRadius="6,6,0,0"
Cursor="Hand"
VerticalAlignment="Bottom">
<ContentPresenter
x:Name="ContentSite"
TextElement.FontSize="10pt"
TextElement.FontFamily="Arial"
TextElement.Foreground="Black"
VerticalAlignment="Center"
HorizontalAlignment="Center"
ContentSource="Header"
Margin="8,3,8,3"
Width="Auto"
Height="Auto" />
</Border>
</Border>
</ControlTemplate>
</Setter.Value>
</Setter>
</Style>
Hopefully that is a nudge in the right direction; you will still need to add that as a style resource and reference it from your TabControl -> TabItem.