If you want to annotate the operating point you need to:
• do a spice .op simulation
• write results in the raw file
• in xschem: Waves-> OP Annotate, load the raw file.
All net labels will show a voltage (so give a name to nets using lab_pin.sym instance)
All voltage sources, resistors (and ammeter.sym) devices will show current.
You can also annotate voltage values from cursor position in a transient waveform:
• Do a spice .tran simulation
• write results in a raw file
• place a waveform graph: SImulation->Graphs->Add wavform graph
• Enable Simulation->Graphs->Live annotation with b cursor
• Load data: Waves->Tran (load the produced raw file)
• correctly zoom the waveforms in the graph (see
https://xschem.sourceforge.io/stefan/xschem_man/graphs.html#graphs )
• Add the 'b' cursor (press 'b' inside the graph)
Moving the 'b' cursor you will see the data in the schematic at the cursor point. (edited)