Plasma spectroscopy is a versatile tool for diagnosing key properties of plasmas, including those generated by discharges. It provides critical parameters-such as electron density and temperature-needed to optimize plasma sources for laser wakefield acceleration (LWFA). Stable, uniform plasma channels are essential to sustain GV/m wakefield and generate high-quality electron beams for advanced applications like radiation therapy (RT). Accurate spectral measurements require reliable wavelength calibration, as optical components can drift with environmental changes. In this study, atomic emission (AE) lamps-specifically mercury (Hg) and neon-argon (Ne-Ar) were utilized as reference light sources for wavelength calibration of a spectrometer system coupled to an intensified charge-coupled device (ICCD) camera. The known emission lines from these lamps ensured high-precision calibration across the relevant spectral range, facilitating accurate extraction of plasma parameters. This precise calibration enabled the determination of electron density and temperature through spectroscopic diagnostics, which are critical for understanding plasma behaviour. These measurements contribute to the development of gas-filled capillary discharge systems for LWFA and support the experimental objectives of the I-LUCE facility, dedicated to exploring laser-plasma interactions and advancing very high-energy electron beam (VHEE) applications. Monte Carlo (MC) simulations were conducted to assess the dose distribution of VHEE beams for RT applications.