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I had a hard time with soap because of the namespace. My suggestion is try doing the same steps on UI with the appropriate role.

Thanks for the input .We're able to populate the field on the UI using admin role. On my testing as well, I've used an admin role to send the soap request and the issue is reproducible

Are they populating the value or the select field ID?

<itemList xsi:type='tranPurch:PurchaseRequisitionItemList'>
                    <purchaseRequisitionItem xsi:type='tranPurch:PurchaseRequisitionItem'>
                        <item xsi:type='platformCore:RecordRef' internalId='4'/>
                        <quantity xsi:type='xsd:double'>2</quantity>
                        <options xsi:type='platformCore:CustomFieldList'>
                            <customField scriptId='custcol5' xsi:type='platformCore:SelectCustomFieldRef'>
                                <value internalId='1' xsi:type='platformCore:ListOrRecordRef'/>
                            </customField>
                        </options>
                    </purchaseRequisitionItem>
                </itemList>

this is how they populate it