The following is from my WIT template. I just confirmed: This works in Visual Studio but not the web interface. We just applied 2015 update 3:
<FIELD name="Subject Matter Expert 1" refname="Microsoft.VSTS.CMMI.SubjectMatterExpert1" type="String">
<ALLOWEXISTINGVALUE />
<VALIDUSER />
<SUGGESTEDVALUES expanditems="true">
<GLOBALLIST name="RequirementsSME" />
</SUGGESTEDVALUES>
</FIELD>
Global List
<GLOBALLIST name="RequirementsSME">
<LISTITEM value="[ ]" />
<LISTITEM value="[David Jones]" />
<LISTITEM value="[Brian Adams]" />
</GLOBALLIST>
<Control FieldName="Microsoft.VSTS.CMMI.SubjectMatterExpert1" Type="MultiValueControl" Label="Subject Matter Experts" LabelPosition="Left" ></Control>
The result on the Web interface is an empty dropdown.