The rapid scaling of large language model training requires distributing GPU resources across multiple data center buildings and regions. We refer to such paradigm as "scale-across" training. As infrastructure expands, the system design space becomes increasingly intricate, encompassing new model architectures, hardware heterogeneity, and evolving communication patterns. Drawing from Meta's production experience, we highlight the complexities of deploying training jobs across a few data centers housing hundreds of thousands of GPUs. To accelerate exploration of the large design space and to enable efficient training for frontier model development, we conduct in-depth characterization of three key design dimensions: parallelism placement, parallelism scheduling, and network layer technologies. We then propose ScaleAcross Explorer, an optimizer that considers the interplay of design dimensions and holistically optimizes scale-across training. Testbed experiments and simulations demonstrate up to 64.62% training speedups over production configuration and up to 37.59% training speedups over the state-of-the-art baseline across a wide range of design points.