Selective agrochemical spraying is a highly intricate task in precision agriculture. It requires spraying equipment to distinguish between crop (plants) and weeds and perform spray operations in real-time accordingly. The study presented in this paper entails the development of two convolutional neural networks (CNNs)-based vision frameworks, i.e., Faster R-CNN and YOLOv5, for the detection and classification of tobacco crops/weeds in real time. An essential requirement for CNN is to pre-train it well on a large dataset to distinguish crops from weeds, lately the same trained network can be utilized in real fields. We present an open access image dataset (TobSet) of tobacco plants and weeds acquired from local fields at different growth stages and varying lighting conditions. The TobSet comprises 7000 images of tobacco plants and 1000 images of weeds and bare soil, taken manually with digital cameras periodically over two months. Both vision frameworks are trained and then tested using this dataset. The Faster R-CNN-based vision framework manifested supremacy over the YOLOv5-based vision framework in terms of accuracy and robustness, whereas the YOLOv5-based vision framework demonstrated faster inference. Experimental evaluation of the system is performed in tobacco fields via a four-wheeled mobile robot sprayer controlled using a computer equipped with NVIDIA GTX 1650 GPU. The results demonstrate that Faster R-CNN and YOLOv5-based vision systems can analyze plants at 10 and 16 frames per second (fps) with a classification accuracy of 98% and 94%, respectively. Moreover, the precise smart application of pesticides with the proposed system offered a 52% reduction in pesticide usage by spotting the targets only, i.e., tobacco plants.