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this.gridGroupingControl1.TableDescriptor.Columns["Col2"].Appearance.AnyRecordFieldCell.CellTipText = "the column tip";
But if the tip is to vary for cell to cell in the column, then you would have to do it in TableControlPrepareViewStyleInfo or in QueryCellStyleInfo.
//Way 1
void TableControl_PrepareViewStyleInfo(object sender, GridPrepareViewStyleInfoEventArgs e)
{
e.Style.CellTipText = e.Style.Text;
}
//Way 2
void gridGroupingControl1_QueryCellStyleInfo(object sender, GridTableCellStyleInfoEventArgs e)
{
e.Style.CellTipText = e.Style.Text;
}