This should do it:
SELECT *
FROM PENDIENTESCOBRO
ORDER BY
CASE WHEN NPENDIENTE>0 THEN 1 ELSE NPENDIENTE END ASC,
DFECHA
This is because you can use CASE espressions in SQLite ORDER BY clauses. The CASE I put makes all positive (>0) NPENDIENTE values have the same order value... so rows are then ordered by DFECHA.