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A new approach is required to determine a technology's value to the power systems of the 21st century. Conventional cost-based metrics are incapable of accounting for the indirect system costs associated with intermittent electricity generation, in addition to environmental and security constraints. In this work, we formalise a new concept for power generation and storage technology valuation which explicitly accounts for system conditions, integration challenges, and the level of technology penetration. The centrepiece of the system value (SV) concept is a whole electricity systems model on a national scale, which simultaneously determines the ideal power system design and unit-wise operational strategy. It brings typical Process Systems Engineering thinking into the analysis of power systems. The model formulation is a mixed-integer linear optimisation and can be understood as hybrid between a generation expansion and a unit commitment model. We present an analysis of the future UK electricity system and investigate the SV of carbon capture and storage equipped power plants (CCS), onshore wind power plants, and grid-level energy storage capacity. We show how the availability of different low-carbon technologies impact the optimal capacity mix and generation patterns. We find that the SV in the year 2035 of grid-level energy storage is an order of magnitude greater than that of CCS and wind power plants. However, CCS and wind capacity provide a more consistent value to the system as their level of deployment increases. Ultimately, the incremental system value of a power technology is a function of the prevalent system design and constraints. [ABSTRACT FROM AUTHOR]